NYTIDNOVN woodvA TM wOnIPA wanogy Adoosonoadg ze[noojopy pue Anstweyo umiuend, «sun Is) fp aUINJOA, Asrumayy [essdyd Jo NoomAL Vg ‘sonueupomaqy, 2 A sung anumey ‘do aeumog OME JO SAIS : J unjo4 Aaisuoy porsdyg J0 1009.0,-A ©KL Kapoor, 1985, 204, 2006, 2011 ke Fourth edtion 2011 Reprinted 2013 MACMILLAN PUBLISHERS INDIA LTD ie by Amitabh Nagpal for Macs Publishes India Ltd, Floss, DLF Corporate Park, Gurgaon 122002 (Hatysna), india ighthas been inadvnely ings, pease nly ie bliin writng fr corte aston, To ‘My Mother and to the ‘Memory of My FatherAooiey 9 ‘woueBeanoaus wnsuos pu uoreoaidd aay 03 nung PE IyqEINS Pte kdoasonseds senaejoyy 40 sao among snaosy "srando anu kdeoso vore0 3 sos ou waBou fe ms pur y yo Poe aoa uonsginued Jo Sep apNoU SSH, ‘PIPE UDG ANE nvouue Se seneju rudd euonpe a pIsoqrsuoNoy dey pus UU 28 R09}0W4, Papua sIdeND MAU SAPNA yAIUNIOA JO VORP MOUSIUL + 5 Jo uoreausp am pu sjoquks win senoojcu pue 2/uOR 30 2F9P J0L9¥ oso sopjsoq ‘stun ayo pur svoelado wnivowour seine ory puz wopezrueng Ate “oIueOVY ane JAE tp pap Stem SEunxaune JO uy ap u spoyeu swoWwa|ddas ‘voMpa puodes 2p Uy ‘ovffnamp posn azesyun 1s. + joureu onusansés stow vu xo tp pusistopu of J2pead 24h EF 01 SSupeouans sedoxd oxy yyy pawasaid usaq sey Jae 19afgas AUS ay, « “ssi Suouepuatswosas yan ay seresods00u1 409 tL + auyeay Buoy}oj ay 0}90) 7 SHIDLOA 30 vowpe pasynay ayy ‘stdoyp jo yung] WEW 21p SUEGIMSIP MOURA, W2¥8Kid JO rag a roojowosoew pur sojueucpoutoyn ms spc} noun " Noosoaoads sn29}ous pure ‘saquadeud ajouSew pur [e91s199|9 “Suspuog [earwayp “gmnssare ue sds ppm pen 0 WORD YIN 9p 0} ovJorgPreface to the First Edition three types of problems with different objectives in view are listed at the cach chapter: (1) Revisionary Problems, (2) Try Yourself Problems, and (3) Numerical ‘smeeaisarun areataz0¢ Bade0>, ysUEIL 2onDay XI amy (67 ummUaWOYy Buy or paddy poyray soresado-s0ppe1 941 MA emeouuy 987 SUN IRwWOIY TA oY 59) wory vafexpsy Jo uonsiby JeFUpONDS Jo HumNds [A Bou £9] sarPuIpioeD repod jeouDHAS OF SeUIpIeE.) uvyseneg wosy 10}850d0 ueI93} 110-0185 Bupa ory sabe SH U5 Avinsomny ALemmouy I eraouay out PPE ay) PUE PONaWY seUAS JBNO 10 awoUEH ® 20} von ZPupans jo ZIT wou0yy anoufeyy am pue wmUSUIOHY IINEUY Gy (66. soteeds 247-0961] 20} suonNaLASICS Avsuoey Kugigeqarg pur stonoung aanys jo SuoneUasaiday jeH0IIg $1 og wory waBosphy ayy :ioug 69° satnsajoyy nworec J.soug YeuoRBOR Jo VORA G1 [86 _S@zou3 feuoneyy Jo wonezTUER) ST Ze $Sroug feuonesueAy jo uonerAUEN YL Of Asoayy, 24n}4 298upanos ET 2g wonoora ayn yo sum 2A =P SPIUNOL TI 1 Gaoony, umn? spree, 1 ‘AMLINLLS UNOLY 1 (GNV NOLLYZUINVNO OWING 'SOINVEDAIN AVAL "T 2 somnpa t8ng 24 0 201g m0 oma Panu 248 01 200P% $}U9}U0> nares onasatsnneRn Ron 004 to0de 19 S861 *B20H1 mpd #29 100 pr swwauo> “yo que 20 404% kue 04 20) eumesg 2pm Au oF 08 syueey roads oy vag i i | i spreito} suons98ns aqqenyea pue “ye 3 Ausssaru 98 ¥ soneojoo pus syuapms Su 01 uo 2 suo fm pio ‘Csmbur oasies yo ds 2 20 wt pomtsur ow "ERI id" Fold oHpea Kuo souporgspur sqea Aus aBpmoMrye 1 yst | 2009 amp wou uous 4p o ats en yy ‘ane se yor i 0p youoneunay uses) sun 1 ip [op sureas dns 30 mote a sons sapstongun if 0 sp F830 Aston amy Jo sosmoo aenpesipu 1 9 9 0 UEMBIN FYOOANa) MosaNd aN WhoRL, “suspis an o someday 205 G00 pas aro oD Sat goad yong “Papcid are oquosoad raeiks a :2yso, pad am eousuma porn 2% jo a8popNouy 9 poo pms a nse pwn nga 29 paar sua Gaara ‘uonenyesa-sfos Ur sywapRIs exp o2 AaTUMUOddO ue pIOYR a evn Popo am oor Seve saa amfuugAnnexure X ‘Annexure XI 2. THEORIES OF COVALENT BOND 220 20 22 Expression of Schrddinger Equation 220 23 Bam-Oppenteimer Approximation 221 24 Two Approaches fr Approximate Solution of Schdinger Equation 222 25 LCAOG-MO Treatment of Hy 228 Molecule 249 29 MO Treatment of Homonuclea Diatomic Molecules 252 Molecular Term Symbols ° 267 Heteronuclear Datorie Molecules” 363 United-Atom Concept and the Carelation Diagrams 268 Hybrid Orbits 272 214 Triatomic Melecules 282 21S Comel 216 Conjugsted Organic Molecles 309 Anesure I Localized Molecular Obitals of CO and Ny Molecules 329 Annexure ML” Evaluat HY 335 ‘Anmesure I Conventional Representation af sp? Hybrid Orbitals 338 3: ELECTRICAL AND MAGNETICPROPERTIES OF MOLECULES 341 33 Effect ofa Dielectric on the Electrostatic Field of Parallel Plate Capacitor 345 i Equation 346 35 Debye Equation 348 36 Experimental Method to Determine crand p 351 37 Variation of Molar Polarization withthe Frequency of Electric Field 353 38 Lorenu-Lorenz Equation _ 354 39 Union of the Debye dnd the Loreniz-Lorenz Equations 357 50 Tonic Character of Diatomic Molecules, 360 311 Bond Moments. 360 Contents 314 Magnetic Feld in a Substance 37 BS Molecular Interpretation of Diamagnetism and Paramagnetism 371 316 Total Molar Magnetic Susce 317 Calculation ofthe 318 Gouy Balance Metfod to Measure Magnetic Suscept 5 Annexure 1 Magnetic Fields 383 Annexure I Expres entation Polarizability 391 . MOLECULAR SPECTROSCOPY 393 Al Introduetion 393 42 (Nuclear Magnetic Resonance Spectroscopy 401 43 Electron Spin Resonance Spectroscopy 430 ve Study of Quantum Mechanical Treatment of Spin ns in AX, A and AX; Systems $27 MOLECULAR SYMMETRY AND ITS APPLICATION 336 51, Symmouy Blements and Symmetry Operations 536 try Elements 542 ions of Geometric Operations $48 Group $51 of Symmetry Operations of a Molecule 552 ‘of Symmetry Operations 559 ry Operations of Point Group 560 538 Reducible and Ireducible Representations 587 59 Characters of aM: 510 The Great Orthogonalty Theorem 584 teristics of Ireducible Representations 586 ‘Worked out Examples of reducible Represer ‘aCharacter Table 592 515 Desciption of Mulliken Symbols 592 Readucible Representation basepoway uous £909 xo ou poo oa, Tsp pu woul w Yate roawoun end UIE age SEH VORP] foamy feos sta, ‘donetpes ojo Karas 2430 apuedapu 290 alpIsue> fen pe ‘one 30 apd ayy 30 abs ayo} twuonzodond se (3sau9 “rv anew apouleonsye 9 0 pabapsuns Ses 961 PHBL HH OHI Nowviavd Adoe-xOV7E ay aon pa Frouea er pandde uoyy ious yo snowayoq wiramenb a3 uo pase A1oom 4 toes on any ay) sem young ey GS0oKp JON stHOs 30} YOHaS af O Par STL ‘soofgo Tews Jo ano1Aeyoq a} 20; now a aN se ADAH TOAST 3H 1g panna eneds amsip 2p pu ef 2m JO ‘sloweslosqo jusuruods jo qn v Yomuse yuosi2uu ox Jo sane] amp SENG fpog 19018 e Aq pons, suoneipey wwore}peH Jo ‘Aaoou eo}9Se19 vononponut AMO3HLWIALNYND SAEVMOL Hb aaNjan.g sWI0yY pue wonezyuRnd Assoug ‘soTUBYIITA| AAC AA I oe xepuy Toe seaeysy yea15 pur suossandyg oneMAKMAYaUiOg. = xpurddy 469 swoIeg woIsIoNUeD puE SII) =| mpuoddy 689. sega soEEID PosN fYUOUWOD diio§ —axmauy (049 swaurvosirg Tepeweae, Pu" apoqog UE Yop 30} UEP UOREHIE 45 199 tensed © Jo Smyqegoug Zunotpana ¢zs 959° suonoyy uae, Jo suonewesaxd>q otaronpauy Zr¢ 659. (eden we yo ony 0x27 Burampary ize 829. SENRIO PAK Jo VoNEALOY Ore 129 wreks oehoonsy 30 SIEIO TINOEIOWLL GTS some ape2 A Textbook of Physical Chemisiry Fig. Variation of intensity of| ‘Two Fundamental Laws of Black- Body Radiations Various Attempts to Construct the Spectra nent Inseniy fzaiaton al theory, attempts were made to explain qualitatively ature of the curves depicted in Fig, LL. Two fundare {ows regarding the nature ofthe curves were established These ae docoubaa Stefan-Bolteman law This law was es conting to whic, te itesity of lr Proportional tothe fou power of he kel Ez oTte (24) bs wer ois 3 consan, know 5.672% 10° Jn? SK. Subse thermodynamic principles by Stefan, (Ghe area under the curve) is ature T, i. ie is found to be was derived by Boltzmann using Wen's displacement law Accowtng to this law, the wavelength 2 at ther Pinus. 8° #22 isebutin is inversely proportional othe tmpernare Thus Agu T = constant (1.12) Theoretical attanpts were also made to the shape of the energy spectra tis emg of Wavelength. We describe below te te important torent this dieetion, Wien's co assuring th size, Wien ation Based on the classical electromagnetic theory and oscillators from which the radiations are emited ate of molec, le to obtain the expression B= Sexpe wai Free biar) 3) cera the enemy emited between wavelengths Aand 2+ and a and bare constants, It was found thatthe above equation curves in the low wavelength region, by wavelength region (Fig, 1.2), 8 very good fitting reproduce the res ‘and Atomic Structure 3 Wave Mechanics, Energy Quant range Land 44d per ax dn = SF aa wate avelegth eon is equal to (mE) ad is The energy deny in his waelegth ei Baia eqgal to £42 wh. she comesponding energy ened. Ths, we E,dA= (dn) E a of dn and E, we get Substintng the exresi (in az (a) an One nk # Accoring 10 Eq, (11.6, 6, the wavelength, Hence, E, conics to 6) is found to tthe experimental data a the high wavelength s completely athe ow wavelength eon and ths leads to wht is violet catastrophe (ig. 112). a6, Hence B= proportional tothe fourth power of ease with decreasing 2. Keeping in view thatthe Wi egion and that of Rayleig 3 intermediate expres range of values of 2. He derived the expression: aan is very much Behaviour of Eq. (1.1.7) at low values of A The factor exp(b( A) is very(! aye ata om (: a nee (#5) =09 3 Ws, sal on (611) ba uy up 30 uowsanno on poe (HTT) “a BonMDSANS erry oxen song aH OBE x on) Na se panoud aq wo ve aetret N N ru + (aylw + (g)®u] X= [oot xe e nen] = [-+G0%+ ous oO T=2 pm sa Boyoxiua 18 om N wwe nye a woa8 61. &@row9 aBesoAe am MON, 5 aimonuig snacry po wopiysiondsKBinu ‘sonUmyDapy 20 oneieu _sueop-ybjiorey, ‘1 uonanpou ‘YanBuojonem we porwr A61003 ) 30 worsuedya amp ours x1 “GTN 198 da @TI) ba bg wou Wy Sumunsqng, {W'S <1 Sowyos0 yo squint peo, ‘smo. Se panna 29 ues 0 ai Jo AfsouaaBtzane a woIsaudx9 SMH Ml 1HI5U09 w su atin Cys 6x0 % = J asmneday 1 9 KBsoua 01 Bupaoo9y sores am yo 1 8 pacogdina2y ‘snp Jay {efon we 61 w poe soveoso mm a 30 ABtauD am st onan gu='3 £9 vont Bawey sore>s0 Jo qu ai nef uO | A@soua aferane tm anda oy worssaxdxo woe c ‘Siow wunurupu 2uos fo pdm yousory 2y Bow fo nou kun 9304, 9H “ynser 241 ureydxa of 29p30 ur y>pour "woutiper Spo9-y2HI9 "8 = (9) Popwond pra 3% Lh WOH Youre gy gw? Te 'bg ur woneya) ahoge oq Sun SF +1 Gripes 8 wont 9 089 (y/q)de9 uo aq) sm pu anqea ems © asey Deeg wasn an WB 8 Y BLY Jo somon YY 0 (CT) “by fo mojoyeg UT Pa) von sys 9 (arnrtio £ ary 01 soenpar (11) ‘ba ‘womeps axoge ap HAN (arigebe = 1 Urraytxo ‘um Kea am snp pu ‘900 wey oH wept uorssaxa ue 2018111950 2tn jo ‘6103 @Be10ny your} 30 epow reojes0oys Kaspucyy poostyg fo yoouren ¥6 A Textbook of Physical Chemistry ously—aa assumption ofthe classical theory. In the shove approximation, expenr) © te & i and thus B= 5. » our # ik if a In ocder that Bq ould be reduced to the Wien Wien's Relation wavelength regi, Plank sso tok bal ten te ¢ state tat Airecy propor othe fequency of te adatom a chy Where is the Planck's constant and has a value of 6.6252 x 10% 1. Since v= 1A, we have coe 2 Substituting Eq. (1.1.17) in Bg 1 we have With the above bak from a black body as a fui of wavelength, both in the a high a we have " Hoe aS) a (#e)] exp(-he2ir) =0 ‘summary of Planck's Contribution Problem 1.1.1 Solution Wave Mechanics, Energy Quantization and Atomic Structure 7 Thus 94 FE =O oe are He constant 5k ‘This expression is, in fact, Wien's displacement law (Ea. 1.1.2) Planck's contribution may be summarized as follows: £7) may be reduced to Rayleigh and nck assumed an do 50 In order that the Planck's equation called quanta n may be reduced to the Wien's equation bution, radiation law, obtain the Stefan Boltzmann law E = o°T“ where is the total cation energy from A= 010 Aso, Le es fearon" Gree f ‘The Planck's equation i she Fa Biexpihc ART) =) Let x =helAKT. Therefore AvsholekD and da =~ he desk ‘Substituting the above relation in the Planck's equation, we get Iiegrating the above expression from 0 t=, we have e-faw- fas | Skeyo suo sepia sms 5 3908 JO omen ap aEEp o1 spOUTA tp J0 200 20 "pamesion souejg am oa ado Hi 90m BENS w SPM rte tp Jo 6@x0ue anu] ‘soja suonoe}> yg wo2 ar or jou a jo Fuanbayy sns2\ sUOH} fo wordy -uoneypes waprot 2tp yo Kovanbayy ap a 4 panna oi so KBzau9 onouny a WN papmSn0D a9 AL tay ay =a 3 Oey ea anv 2m (HET Pe (OTT) sb BuHEGHICD carp ax Jo uy oswoxouy ep sepv0u9ur popu stro JO FogKN 2H ‘SAL biaip uo 204 pire panwa suon22[e Jo JoquTs 24 1 foo 19 vam mn od you a SUPRA wyuenb Jo Aqui omy woot 28 "WE caaay ain A484 Jo A4ysuzpe ap uo 708 poe LORE ‘vo spuadap svonsap Jo ABsou> oneuly =n vet SO “uot sr 0} SBraU WL ne wonooye a % ue yes erp any an “0809 pengns 2q ue wonoof amy Souenbayypyogsus 30 st UoREPE? 12 7 4 rr wt au 5 ad Da ‘ yo ap oe wonooye pongo xp Jo Kua xn ‘snore amp 30 Ezan0 ep O1 To oonbse wonDafe atp ‘eu 241 Jo WD! a Ms Sepmico WIONA SD UAL A (01 nbs £81000 feo sated sjnoip Jo dn pene 2q 01 pats Boykoydts q 18x amy yo Aowenbayy ag wo von29f2 paNTID oR 50 asoua apaury 0 epudap amp pe Zovonbay progr 0 2uateH9 “uO ]0 6 asmonug nuory pun uomomuond Bin ‘MOyreH 0A ‘suonoera powiwa yo AB1003 NUD paya auporooiedd oa ‘WSU ‘ossrue soars a 24 ‘a4oge pats nay 2u922qeoqo4d Jo SONS ARIES “sm qsuo. st wo spuadap ueoq wy 2p Jo ABsou9 amp “Sz0a e ‘Brana o2uny pe KBiou9 paras ‘24901 penbo st uonsoyo amp 03 30 Bsou2 9n0URy 24, Aysu>}0 SH wo YOU uP ‘1p jo Sovonkayy 2x9 uo spuodap suonsoto pons aq Jo A@isU9 aNA0P| a], « “Kouonbaaf poysany am paqe> Souanbay, tunaurar aus wey 2,08 20 07 fondo Kouenbayy Jo uoReIpE iv pompEA a1 way are perow anS e uno KjsnoauzreRsu ponruD ax SUON29}9 UL, & ‘panrsgo are sonsuaoeqp Suojo} 2, wo ST 8 Jo uo € Uoye MMe IIS PAE ‘eo ¥ wy AjsnoouRNEU paymHD axe SoONFA|9 =p YaayD owIAA}DCIOK 3p YL s ot coats spam a Bnaabont uy Tayssooons sea 24 8H Jo aTEU yNOsNAO> am NYA Ay 01 Tonba ABsa09 Uo ayGaeo uopoyd yoed wpm aumgeu wr ejposndicn 29 o} axe WBN a pasgpIsu0D ‘rou ‘mi, ‘suonoyd poqe> ewenb 184 Sunssuoo “peznuEND SHER PD Yooys 2eF—CI0N idx 09 Kou. yeojsser9 jo aunyes su0s993 Jo uorssw3 ain Jo) uowosnbow, ‘61003 oH 2u29}00}0Ud Jo ‘sopsuajoeieyy, Aasqucyy powtys fo youeL V §10 A Testbook of Physical Chemistry Experimental Determination of Kinetic Energy of Emitted Electrons Decrease of photoeectriecurrent withthe retarding otentiat Example 1.1.1 Solution ‘The kinetic in Fig, 1.14, increased ‘of emited electrons can be determined with a device sho this method, retarding voltage is applied and its value is electrons from the metal plate each the col | ‘The electrical work done inthe above process is Ve, where V, isthe retarding Yollage and is the electronic charge, The electrical work willbe equal to te netic energy ofthe electrons. Thus, we have 1 Vex d mits hy hy, hes g mite ky dy (ia) (a) Calculate the kinetic energy of a phorolecronemited by a sodium surface when ‘wavelength 400 nm is incident on it. The work function of sodium is 2.28 eV. sue ofthe longest wavelength Which ean result in tcf he gest wave tin the emission of oF ms") =4969 «10s Based on ‘of Equiparttion of Energy Disagreement with Experimental Fact Wave Mechanics, Energy Quantization and Atomic Structure M1 ‘The wok funtion of sodium is Bye 208eV = .28e¥) (L602 «10 23.653 105 [Bnergy cared by the electron is y= By B= 4.606 (@) Wavelength of te incident phot je 6b 0 ‘work fonction G63 x10 25441 107m = S441 om HEAT CAPACITY also showed thatthe problem of variation of heat capacity of mor ith temperature can be resolved by employing Planck's idea of quan The monatomic solid may be considered a cof oscillators with thre: ‘vibrational degrees of freedom. On the basis ofthe classical law of equipatition ‘tenergy, each oscillator of such a solid possesses an average energy equal 3ET. ‘Thus, for one mole of oscillators, the molar energy is E = N,GET) = 3RT Since Cy = @EIOT)y, we have Cy =3R ‘According o E (I.1.28), monatomic solids have a constant heat capaci {03R(a vale which was obtained empirically by Dulong and Petit) Experi itis found that this value of heat capacity is observed only at high tempe 24) ical theory, the heat capacity of a monatomic solid should ever, does not agree with the decreases with the ations for Pb, Cu, Si experimental fini secrease in temperature, Figure 1.1.6 depicts such and C. By employing Planck's idea of quantization, Bin vatation of heat capacity with temperature. He have vibrational energy which is an integr in was able to explain the Bane oven 126) frequency ofthe oscillator and vis the smallest allowed frequency scillators are not vibrating withthe same frequency but have value ‘an integral multiple of the smallest frequency vp. The numbe sessing the frequency Vcan mined from Boltzmantse my a4oge 2yp Ka poonposdas 24 uafeaphy om Jo we ELOY ue we Orep “ud Lo-9gy “HU ‘atqeasesqo oy ome ‘s Sat san wos oe oro same so so siren oy fq arse 8 satep ogy ot in pose serenop 4p otoovey "oy en 95m yom sseanapandey —— se possadio oq enoedg uaBoupiy wnoge x Aq s6uppung rrp rewounedeg WoLV 40 7COW uHOA 3HL facet soimproduioy we= ite ="9 son a wen07 ney am ‘Soi ‘Pato}H0U 9q UPD om ueYp ray sromod 2m ‘soamesoduia moj 2° Jo onyen Bul ‘um sual oy pur ffs A294 St Z4/%ay “2 Jo sonfea YBIy SpustonTS iV ‘ononbo was se unouy (oz) f+ cen’ sn o} oO ent Tay + ar 5 Aomdso wy ajo yo snea Sxpuedban an poe ; [eave ey aayean+t] of We(go'Nea ‘2ABY am YoIoey JeUaUOdKa amy Supuedysy eT) FEC ay dx ay t= Cenandal pay) 7 capes (oy) P89 8282 Saran ~arrayivo yom 51 ay sore ap ve os yBoUD YBly ame 19 2 1 paonpas aq n> (67 3 ‘ME Jo ane feqsse ap 09 s8ea23U org warmers gy w 288 agp on 30% yoanqea ap uodn spa | 4Wave Mechanics, Energy Quant 14 A Textbook of Physical Chemistry model of atom in which the ee shovwn in the following ne us ou ne nce ed ea nr radiate cc tous energy. By losing Slav wulcome nae an ete he ake nd enc. Thw gives ie fo a able oma Anfnan = 486.07 = 364.56 (. ern ; sn which contradicts the experimental observations (as at at 2 ( Sain acm cnt i : e rimer ‘determined discrete spectra. Aan 2900 «36455 (5) 6496 (2) «aco ea ng Pack’ idea of qutzatn of sled te sore problem by aso tom 2 Tc ng vo a cou ee cal cea oe sent systems of atomic dimensions and, therefore, it has ‘tarot adequately epeset 5 Set eo (Le 36 and Ayfom = 41013 = 36456 (©) - (¢ . Fae] 356 (B) «ato in the frequency nit, we have Expressing Bg, (1 meio tt (G56 107 m ich appears inthe Such that Av is equal t the difference in the energies ofthe two sates. can be generated by imposing ‘Bobr showed tha the allowed stationary the quantum restriction on the cascalexpesion given by Ea. Rotherfrd’s model. The quantum retition proposed = GEES mf wae" (F-4) Since nm, =2, we have ay ie uit of rromentun ofthe eevoving electron rile of the bas ™ wa Ohm) ie B56 x 107 @ Z on a (3-4) mere "\an) SP SEGE a) a.) svete nthe mmiber of quanta of angular momentum andi knows asthe quantum, umber! The number w can have only integral values auaton (1.132) as sugested by Riz. The constant ys known asthe Rydberg Const for byogen and has a vale cF3289 83 10" Hz (1.09737 10% Prana ttt Model Ts the Rutherford model ofthe stom, econs revolve around the sueles in ch oftiekogen Atom — way thatthe Colonbic atracion ofthe elton bythe mews tle by oe which ends fo pl the elecion and nucleus apart ie ) force = centrifugal force Ts qn binging energy Tis quan ency of rotation ofthe eeron fn an in terms of frequency of rotation is 33) KyTEND oq, werd ee: am op 2 ehh ero one eens ow upey asp 3 ane 90 sit, (at) 2, iCemn ieee Set out) 198 a8 (EET) “baw worsandso ode ap SuNSGRS ‘anny om sO AaeuoneIS 1 sh toujours 4 pou 99 ED Jo snipey ta scaspuoyg porskyg fo yooqna, ¥ 91 LL aumnayg snwory po woyrinuonts &Bs2ug “OCHO 2htization and Atomic Siracture 19 18 A Textbook of Physical Chemistry Wave Mechanic, Energy Quantization and Atomic Su Energy Expression Now according tothe Bohr postulate, the stom can emit radiations only when the for the Spectral Lines: “hese spect ines can be generated fom Bq (1.1.40) by giving diferent values to my and ty Thus, we have Lyman series Balmer series Paschen series Bracket series fund series ‘These are also shown in Fig, = a 8 ee oe Wy 1 where Ry = 2n?metMi®(4ne)?. This \n is, in fact, the Ritz equation nts eae eaten of Rydberg a ea = 3.2902 x 10'5 5“ 1 o Ra = 6979 x 10 mat 7 HOT 2% 10 wt i remarks about ‘may be made, The Bokr'stheoe ‘The value of fy is vey close to the experimental value of 1.097 37 x 10° en Bohr's Theory ws Tore, Boht by itoducing quantization of angular moment a - ines of hydrogen atom. His theory can very We ‘Spectral Series Five spectral series of atomic hydrogen are known, These are: pecan aoe oan pect lines forthe hydrogen species—species containing on rman series Lies in the ultraviolet spect eon. However, completely file whe Hydrogen Atom uy Lies in the ultraviolet spetal ae Balmer series Lies in the visible region, och as He* and Li, Bol’s Paschen sees Lies neat infared region. Bracket series the infared region. fund series the far infrared region.fo2arg2 Poy pm paige 4 ate ee oy aon tang ones = am euxorao pasnnoo xp SO, 7 Sut popes om ft NORE re ape 999 foo 5, 349q 61 woRSANN!Y aw ON sayaeay) sojed am por 69 pooeydat ret Sessa pomp a 54 : 0 rn aoa os FATIH ta 2 uodsaiey urna wnt © Jo WHS iow) sre Ot cy dou) wo J Sea a ang a8 CTT DI PTT) Wa BNO] 45 5, 2 sono) peings09y ai” oor eget =a (vd ‘ or yruodsasso suossanixe 0 72) OS "o ejuou jo quouou a S17 4 anu eBnyuon pe £8109 aay 2 0 ue eens @ uf “yno=gou A (12 Mo (te = of 22 }o ol thee ‘on sotgipoms (24°11) “DAL “SL aries oe ang 1-1-8 8D 4 amueo yo woRro0| a WOH UOH=ST? se zomanus agony pun women u01 SM? 07H, wna sey AG) = pus aut) =a So! 1 [pUEDE/KS JO qn) wpe jo Sombra Suess 308 ue Sstnen pez Jo DUET ‘snes aad a ‘wogmova! 200 of “paoey supe mt ponds. "wRNULDD A ‘2 pu uond tp voameg 4 sump a J0 sur wy possan oq uo % pues ‘eaves a, wren! pov UoHs> 030} as mp stay Kysop eA a aH, crv oftuso}tu=7 omy om sm, Sse Jo vrosd ax 0) pu “see 30 uanooye 24 3 Buenos TEU FAHD 2 30 ans ano obo 5 wuns2WU eB ENG TOYA wove ary. a JO wr su = 400 = uonsojaay Jo wnuowou ree [eHO aN HON, 4o=a woyssaxdxo we £97 ! nue sy yo sun 1 possaxdxo 2q una tujod © punore Sunjonay pane © 5 JPO0T 9 somos se pasoud og eur sta, 58 pauyop ‘wor amp Jo sseus poonpan mp *w uoMDa.2 40 sseur amp aoe}dat on 51 9peus 29 01 8un4> Ao ayy, PasopIsuOD s Feu Jo aU ‘wou 24) punom® uonoaye pu snofpnu Hurafoxat Jo sage} aAoge a J YEA ‘atovfeun strewiar Asoo 8.4 Jo WSTPUEI] arMUD a4 YL WMOHS 29 HED If ‘uaoys se 'seoused on 19 Su punose ujjosar ase uo ay am Jo asmeo9G“H pn 2930 ‘sne}onn ‘up jo sseMN UL 14 >u1 UY Je} OS 94 40) UOND_NIOD usury porsiye Jo yooanay ¥ Oz22 A Textbook of Physical Cher Example 1.1.2 Solution Example 1.1.3 Solution Example 1.1.4 Solution ay Calculate the sped ofan electron inthe fist Bobr ott ofthe hydrogen atom. Given: ay = 52.9 pm, We have Sh For the first Boh onic = 1. Hence ie) (529x107 Calculate the ionization energy of the hydrogen atom. ‘The ionization of an atom isthe enersy sequired to knock ou the electron completely fiom the stom to give a postive ion. Thus, inthis case we have =218 103 (Calculate in eV the third ionization potential of the Lithium ator ‘The third ionization potential means to knock ot the lat single electron from the Li?* Jn, je. Li* > Li?" + 6° In this ease, Z= 3 and thus, we have “eee Cle) Using the reslt of Example AB #9 x28 x 107 3, we get = 1962 « 10-5 4, we have Since 1eV = 1602 «1 1.2. TOWARDS THE WAVE NATURE OF THE ELECTRON Wave-Particle also possess particle characteristics, The converse of the above aspect, vi ‘material particles, whether big or small, possess the wave chara : proposed by de Broglie. The relation connecting the characteristics of wave and particle nature of radiation nay be desived a flows Wavelength of an lectron—A Specific Example n and Atomic Souctare 23 Wave Mechanics, Energy Quant Both the wave and patcle nature ofthe radiation are associated with the energy according tothe following relations be gabe Plancl’s relation oe 23) of pane mature (ema =) each other. Now cin wath 2) are iaversely related 10 the photon, and thus me may be considered to be the joton. Thus, we have For ordinary material patil to be equivalent 10 v (ie. the 4e Broglie velocities) and thus Eq, (1.24) small, asin the case of subatomic particles, the ‘foe them wave nature is expected. For a particle of ificance, on eclertt tn canple, let clelat he wavelength fran ele Asa aml alloca ¥. Te net ene of te econ woud begs pte eon 2 mvt = eV i snd hs Bement = mvs m(220)” = cmev!? as Ue Cm) 5 (125) ina (1.28), we hve gets tye ~p mevy™ Substituting the values, of A, m and ¢, we have Aim 21.227 x 107% 26, For example, for the potent . = 1207 x 1072 x (300)! m = 7.083 x 10m = 70.83 pm ofthe chapter forthe derivation of Eq, (24) based on iy.wx res ve og ta won yo Ao on ons Buen 1 x PE (aor 01 x sore) % 9299) ety 2% wont aos ap aid (8) wong ya o uapien apse cond as on pauogson 9 uno We Hp jo 9 0 Joe (012 als tw oy popooe wae uoBeeo WE pes aA HH soma EMEA ey 31 (@) yw Tp 9 pfuant 04g ap a8oyN YORE we JO paads a TENA) 01 S80 X O90 x GOT} gawe) Ey oN StH 01 x 90ET= 1 a al + an) * aw © oouy nay an 42 = yaw © aoug {an 00g 30 aauarayp renvarod Ka yessaone uaog st ip ome} UE Jo BuEFEAEN 1/4 9p pu RODdS 9 STIEGN ore Jo {aoa si BuyquoseP a syoR La poonpanN! Sem YOIY UOTE e se (B)eerea » (ve 1) ‘bg uy woneyas s.anoug 2p SuronponD Re aamanag anweay pro voworinamg) (Bio ‘sorum4sey 240A uonnjos zee oduexa wonnies bes odes 29 200 ROM 2A IN ‘foeyppypow euro 2 wen “31 “pusjanea -paruasgo 24 s9xou ueo sopradoxd anton amp 05 fgo wash Aue jo suorsuauTp a seyp JONoys Yom IpAUapPAEA v AADIPUL (1 se yan 05 wnquatton ayy ‘SUH snp # 10} Hon 430g ‘anv ap Jo PBvaFOAOM ep Jo HH 5019p waoys ancy Suouedxa pied-n pov wore uafaupAy, EU 24BM ep “UO 100] ‘uopenbe saffoug 2p 219 Woy ora uomoyo xp Jo psu2fanem a pae|oqe> 0 ‘ape posn Soy], 2ounoH J2}] puE UOSSIAEC, 5 Jo aanvew xem aap Jo uo} Sones8 wonzeaytp © 0} “9A2HOH “to s9 wea auo "ig Kreupuo 30g "kb yp Jo pBUDJaNEA 24 JO FIO soymns aan amp AYA HA aK sep JO suorsuAUNP =P kN J0I0e) UEZOM ‘25u0 uo spusdap souai2n%qu1 puP uoR2eApHp Jo wawouayd jo oueweadde =x, ‘s0sseW 396107 Jo soomse's IN One ‘ayy uo quawwog uonoota Jo o1meN orem, Jo uoneoyrion, rewauuod3, Aassrucyy poosky Jo yoownas V- ve26 A Textbook of Physical Chemistry Statement of the Uncertainty Principle Qualitative Explanation of Uncertainty Principle Fig. 122 Location of the lect help ofa microscope fe 6628 10 03 10m) TexiT "aaa ele 2824 x10? m ‘THE UNCERTAINTY PRINCIPLE In de Broglies relation, the particle nature of the matter is characterized by the {erm momentum p and the wave nature by the term wavelength 2. The two tems ae inversely related to each other In other word related to the stave natu the wavelength as calculated from the de Brogle’s determined experimentally. For such a case, the wave nature may be completel jgnoted and this the particle fas oaly the corpuscular nature. The motion of st the precise value ofits pos also be determined exper ion of the particle can be Aesctbed by a well-defined trajectory. However, the same isnot te for a subatomic particle such as electron, proton, et, which besides the particle nature also have the significant wave nature, The question that whether the position and the ‘momentum of subatomic particles can be determined simultaneously with grest the following example to be determined with the help of = Approximate Expression of, tered photon will undergo a Compton shift. The stectron on str ‘2 momentum and will move in a 22. The momentum ‘iretion making an angle f withthe axis as shown in Fig. 12 n Of the photon befere and after the collision can be calculated from the de Broglie's relation, Thus, we have ‘Momentum of the photon before te collision, he mate Momentum ofthe photon afer he clision, — ape Now, by the law of conservation of energy, we have ened ate Z «2s, toe ho mb b B aed the comesponing expression forthe conservation of momentum inthe fa pedetons ae Foe xeomponent: MY = cos 0+ pcos B 20 by _ hv’ For y-component pin B Eliminating fi from Eas Equation (1.2.12) relates the momeotam wi angle @ to which the incident radiation is def detected ifthe scattered photon passes thro ates may have any value bet ated cone. Thus, we have the momentum of the se ‘which we may call the uncertainty in the value the electron introduces some uncertainty in its momentum value and therefore precise value cannot be determined connecting the uncertainty in the value of x ‘An approximate expression ‘Corresponding uncertainty inthe vale of pcan be derived start Uncertainty Principleojan pu wousod Jo sone astoaud one sp paw 1e9 YASH 2, fondo Ut ages Snap st IUTH290N STL, HH ay Ta voy wd g yo 2pu0 am yo ute st uot yD whe 10) "AL sqrwxo unouy ase wonaop J newt! am pu wonsod ai HOH HOE So spy og sats 1 200) ane aaron © tat 29 youueo fr abasic) 120198 see nt moqe Burge Uy aod Aue Ape sata woop “OR 6 FMOR sersad on panadxa $1 UDMDD 3) tu AGODA SAY MM SEI 798} raneure hy sy. 49 wToHAAUR SUC GoHDATE OTPK MD HT + (ay) (ty) =49 20 ney “mya Arevzoun op Bus panoge 9 ve SRE weiepuodsano> 941 ud yg poe wd 40S Jo sanmea 4 9g PONE oe ay ain uF won oy saue sa 2 es wd ¢ 39 AYoH2ON paurauoep 9g ues sna. oMp wos} YONI 2 ysod om TEM) "oy oye ayo unoe We Jo 359 xy “pdex9 Jo ye, soe asAAE fay 39eors (trquenso 30) Axo. a Pu wosod ap pod see! aane ounnste paujap-% axe ONES "212 ‘Suoqox suoNDdT se yon s3]9N ‘xwowegns rad Speaun 29 30 S2ovanTb2su09 19s 3 JO 200 rags Jane ap stp pu ofgo am Ho paHaHP 0 ue Jo donysad agp Jo woreTUNEI 219 japan ajonsed op -umuawou sy 296 GOTH| su ng yo wag @“oaoge uaes 9 "wasnt Busnseous agp epi sIUseHU} UOHEATES ‘room agdiomad Kurexaodn af 0 ase TIUATEpUN a4, 7H ap JO 809 2D TE ‘pasa pastas 2 we wae 30200 suo snoone Hs PSUNP <8) dp x jog Jo Sone staid popeyouoo oq SeUr Ht sM, 328%] dw rmmpoom tpuodsasso ay feta BK 4H SrURHHEOUN a 25831099 1 UENO ‘ons Aouonbayy gS Jo oda ay 32988 150 211 80 juresaoun upuodseL09 Ge. among nuory pr uoennuond) aawy ‘son@yeeHy * HA aidourd Ayuyeye0un 0 seouanbasuog Senos so gC EE Boas 2) aes sete a ren wlt- G2) =29 pu “vonod put wnuauoe a snuevcun seb cay hee oe Hy ney at aren =. zy Regent awa aon Sanam jo sah bese a, (amuode 19pous Jo adaosouoqut {made rus albsobnas fom 921) pu) SURE 9 2 Pt wMBERIOW an oapen ayy uy AHERDOUN ap (pL 1) “ba © Supsoy “Soo se pond HPD “Smote} se popAdN 29 Kew (S171) pue (p21) ston, wren = AH] (oma)- > savdy ‘ary 9m sm, ae edu oxo Sapcoe ps pfoydua voip ajo winpnes mode spealey ‘sozsas e yap p2ie20} 09 ueD 1Afqo Ue YOR Yl. AaeBNOOe a MON, ) usp W a ‘weamioq anpea Kur any Kew uo aot Sateen ony aa eee 30 wooodues oxp sywasosdan (€{°Z'1) ‘bg JO 9pIS Yo] UL, (9800-22952 2-2 2 DZr0mT- Tadd 0 mod +9 002 = am ama Kasay porssyg fo yooqney ¥ 830_ A Textbook of Physical Chemistry hence a precise rsjectory. For macroscopic particles, classical mechanics may be employed without any derectable discrepancies, 1.3. SCHRODINGER WAVE THEORY Necessity of Wave theory is based on the corpuscular nature of elect, We have seen that ‘Theory ny, besides being inadequate, theory which takes into account the wai distribution of the electron instead of the wel Schydinger proposed the wave theory whic that the behaviour of an electron in an atom can be described by an equation analogous to that used to describe the standing wave systems sch asthe vibrating string fixed at both the ends. An alerative theory was developed by Heisenberg and is known as matrix mechanics. Schr8dinger later showed that the to ‘mechanics, ame, wave and matrix, re essentially the same. Of hese two mechanics, the wave mechanics have proved to be more useful in applications to chemistry. Equation ‘The equation used fr the wave motion in one direction is Representing Standing Wave » System where is the amplitude of vibration at any point whose coordinate is x a ime 1, and isthe speed of propagation ofthe wave, If w doesnot depend on the time, the displacement ¥can be writen asa product of two functions, one depending only on the space coordinates x and ths other depending periodically on the ime. Tus the form of where » Ba. (13, the frequency of the wave and i= JT. i we get “The frequency Vof the vibration and the speed w are related by the eg uz dy where 2 is the wavelength of the associated wave, Substituting Eq, Bg. (1.33), we get Wave Mechanics, Energy Quantlation and Atomic Structure 3i Eigenvalue Problem ‘known as the eigenvalue equation, the function is an mand the constant (~ 47/2, i this case) is an eigenvalue (sometimes 3 proper value of chi ie value). fn order that the (vis an acceptable solution of a. the basic constaits. In the case of a vibrating string ( ‘© The function yrust be zero at each end ofthe sting, at these Fig. 1 Vibrating stringed at bo ends 3.5) an be extended to describe motion in three dimensions by ) by w(x, yt) and the operator d¥/dx” by (36) Equation vive aan where V?is wri ay?) + @V80%) and is known as Laplacian fperator.Itis proaounced as del squared. Schrodinger cei al ao pies Equation sms of momentum by employing, (138)ies oy aq pouosoxdan st poe spuodsoron mado UL, ACA poe ‘one an st, 1 sy panes a 58209 O19 BME og ee ew ¥ squowsoeydar Suunonoy xp & (9 309 sopeado yeogmeyaots nan Surpwodsatos ap on potaxvoo 29 woos Anauenb 2p so wotsssdx FOIHED STL, 2 me QM cg OBE ng ev e wren carpub avira ‘hq vont st g Aron ymOY SH ORE UE uF UOMD9Ae WE JOpISTOD ouuew apduns Aron © a ‘uonenbo saSuipanios ap @anp 0 ayqissod st 2noqe poisy Som SAR BAL srg onqeanaip ann ax we 3728 290} Pu add poasoq-tiom a waxy porenexe {Y) ones woresod3o aM thes sebedl Po paced [ apteyen |” pave l > pans 29 + 40 anyea uormedxo sip woaungusSip we Joep WAOUS 29 He Suysn Sq ‘25eds vorefju09 Jo ool 24 J0A0 spoons voHe ered wos ovo aa a 0 poms 8) 2 nonsnpd seu 10) spams y sone a9 yoy 305 fagoenb sx 3 SOTA fouongo ajo sferaeejousgms ey soredo yy jo ons NORRSDS aU, « sonqes Jo ain 30} uonaunsue8i= Surpuodsanioa amp st » pur *y x pesos 1 onus A vogtuny a uo size *Y wen Aved®y soyesado wont ¥ 304 6 am 01 aqgisod st 1 y_ 58 paraosaidat osp) Ee amsonas spuory po woprennuoni) KBious “SORUDYDORY 240A uuopenba seBurpquyos, yo uonenuod 3 a8 (ang = 42)" ME ag OM eg OME ag ew ey ea a unvowou J suovodao> of Snes opto SUL) x & x 91 ‘ayeUIpIO0 JeAI Jo anjes amp Aq voeoyn 5 sro wntsod apo Supunse vod a () ae a), Sp aop 01 Buposoesygensge eon oeomeetcs eserns oa nd Poe cx aston esto (Seon A loedo enews seu e puossao ra iy 0 oat “tied $9 sone Poser hom aquest Kero Bepeotsaey “snonunuoo 9q osTe Asn vonoury an Jo eaneALop 18m 249 ‘Kampung oan ¥ Aum 2m sup sopisog agen ‘2 Anowgnonp amy puE sn duo © sym voniomny sup 30 a8peqmoiry JOA vorouny w "woisks qwoskyd 1woptedapm am os0U,“sanem 30 uoneZedosd aq oF Buuzajes NOK soyemsod wreie0 oxy paurergo oq ueo (QT'E'T) wonrenbe nem z2uIpanps ay ‘wore we uy wana Jo rug 2p SoqUDSOP YoY opens 1Buponps oWp st (OIE T) HoueNbay a! we ‘amy om (@E1 ba (61) “a BonaNSINS wen G-aue=d 8 0 0= aca De hs ated pov anoury fyo.uns om st wonooye om Jo AGkous feo) 4 woIE we UF wONDD|D Ue sO suomeuess reoqueyson ‘wimuend Asso woes4a fo yoogren VT34 A Teubook of Physical Chemistry Born terpretation of the Wave Function Function toma (Ha) (3) eal} ake, ant a® 3.13) « Rye. va 013.16) Now according to Eq, we have Hav= Ey asin where Eis the eigenvalue ofthe Hamiltonian operator Ha quantity which has a precise value 13.18) finding the sytem space has to be re complex conjugate of ase ai ‘sm enb a (6) pe) sa 0 sos yo an we Yams 6) apa taf ‘a =spracy“al om 4 ps A (ba aS se°staf-o =an°Aty sal 198 om Suneszon ) bg Sousa . vey me 244 Apapoadsas “A pue “A svonouny sp 0 saneatsdia amp 39 "o puna 21 (@) ras s9 angen ap way Kuo aygRenade 9 TH TRA funy oooh | me )— o=aptAta “oy wantaraf tocsoratalo ‘aney om ‘Smt, “Tene axe (¢) pu (2) rung sy 2g onnjog Ze wojaod Eason ooeiyy fo ogra V938 A Textbook of Physical Chemistry Wave Function of the Parti Outside the Box Form of Schrédinger Equation within the Box Expression of Wave Functions St the one-dimensional Schutdinger eq B-Viy=0 aay ‘The function y-will depend only on one indepencent variable, viz, x-coordinate (Outside the box, Eq (1.4.1) takes the form SY me ye art ar eo ys0 Neglecting Ein comparison to =, we bave ey oy idy arnxY War thatis, y= 0 outside the box. This means thatthe particle cannot exist outside the region 0< x< Within the box, the Schrédinger equation forthe motion ofthe particle takes the form Py | 8x'm eet ar Ey =o in Sei ay Ys ay =0 say 2 _ 8n'mE wee? = aaa ‘A genera solution of Eq, (1.4.2) is given by =A sin (0x) + B cos (ax) aaa where A and B are constants. Prom Eq (1.44), a ge number of wave functions siffering inthe values of A,B and o: can’be obtained. However, all sch functions will not be acceptable for the motion ofa particle ia the box. Only those functions which satisfy the boundary conditions of y= 0 at x =O and x= I will be the acceptable wave fonctions For y= Dat x= 0, Eq. (1.44) becomes D=A sin(a x 0)+ B cos (ax0) ‘The above expression will be true only when B =O, Thus, the wave function as tiven by Eq. (144) becomes w =A sin (ax) ua4s) For =O at x= J, Eg. (14.5) becomes 0 =Asin (ad) Energies of the Particle ‘step Responsible ‘for Quantization of Energy Wave Mechanies, Energy Quantization and Atomic Structure 39 1 be true only when ais an integral multiple of x, i. ‘The above expression ce oo s value of n = 0 is eliminated, Sees waco ( aan yeaa (%) vow om (43, 90 van 49 ‘ince the constant n can have only integral values, from Ba. (149) it thatthe energy associated with the mocon of a particle in a box i quantized ‘Thus in the present case, n represents the quantum number The fact that th lowest value of energy which te particle ean posess (ze point energy) is no avers consistent with the unceranty principle. According tothe late. if he partich ‘confined to within a finite egion it ought to have some kinetic ener. veo imprant sep whch is espone fr intaling equation Ma ee eens es, Asting © (148) can vin com) may we jean hve a ae The arin = Ain) a af o alasoluon of Seige equation. B1 With hscopubeson oresysten of pile sv te any sn at ol elas Te facts ch et consist ith sil bs ae ote deadly with Be cresponing va of re wl beer Thus he va of E are ita The Sno tron tony oats of ysng 20 = Be condom tha ce a comtanss mes ine dpe amet ds gen 57 of) where m= 1,2, 3, by “This finally leads tothe quantization of energy which s givv siaqamu wiruenb 20} a5 #305 samt Aagigeqosd 2m PUR SPSL seao Supuodsaso ap roonauny em seo STEEN ZT ANT (1) ap bay (aa) "2-4 scx yyod amp 8 oppaned ap Surpuy Jo Anegegord =U, z "by peso suopounj sab 22I9H'P aes te? sont? woner@aqut wo PEI [fexeenpo-ffee-}o fi soamonag woTssaxde> 24098 2 z =@ 09 +0100 -g-nym Fo wuopenbs omiawouo8n ap FornOTOA wfsb(cefi-wl axey am oevoox0 yo worypuon

size wis aay eran 2. Making wse of the expression ApAx> hi, show that for a re particle ‘ seat whece BE and Aare the minimum unseraintes in enemy and duration of measurement of velocity, respesively. For fe particle the energy expression is pe bmte E aon ‘The uncertainty in energy will be given by sE~25p Wave Mechanics, Energy Quantization and Atomic Structure SI sere Bp i the wernt in p- NOW plo, which is veloc, may be measured by Recang he ditnon Au eaves inte A, sch that zat nh tras the maximum uncerainy in postion ofthe parle drng se measurement of then the sium uncertainty in the value ofp wil be 2(2)4 oe(R)a o2 ipa St ap2(A)L vee 6 = 2 bp SE Bp2 (A) E "h «eat ‘one-dimensional box wit the origin athe cents ‘apr of mass ‘he to + 1/2, The potential energy is ofthe box. The box ex (0 ne, mar Co te ebsing gain the sytem showing separate equation fr th ‘and the outside ofthe box. Sind out it c {) Derive the enegy expression ofthe particle. (4) The Sehringer equations are (@) Inde te box Bey i - =e aon a in the expression Gn) = A sin(aa) + Bos (ax) we get ‘Asin (a2) + B cos (al) = 0 and ~ Asin (all) + B cos ‘Oa adding and subtracting the above two equations, we Bet A sin (ad) = 0 Bos (a2) =0(er cn aeep ord bo seo 293s fs 99 peta senso mato > 0982 seater yon on emo aa on oer 8029 3 00 28 a a ons oats sage 99H 1 (p22 (28) [x22] wn o-eg--(2F]i (oB)4 (Fh ‘on 2 omg “22 ‘os fnuent yeasuoo # 03 yenbo ‘anny anh ZX 69 Sup, ard A (22a lzxe[xe2]za see) oor y ze @ | ye o om eana hig +a (Beth om Zax Gig +ZAN A ns sonoury 20nn a Gz poe CK CK a wyo aiztouene = 2°94 ‘oy om “oy, ffanaadsat 2 poe Cx Jo ques wopeedspay ‘oan suo Seton eo SuOnDny ant 2 Jo rnpord 8 WonDUN A ‘in ‘sig Aq poping “sTeurps009 wapuadopat aoa ype stooany ‘ava ionp Jo pod agp se wants 99 saan a vn Suopuodapor woda Surpuadop wpeo suo) wuo3s1p surewo> soresedo Us IT "rpm & 7 soygezea mtopuadopay sap ayy wo puadap yA wonouny 2m eros ot yg(xe, 22 ct seal 1 wonenbo aBuppayog jo uo 249 *xoq euorsuoup-sp & wy sTonAEd © 20 XO@ TWNOISNAWIG-33uHL ES aumonas 2quony pun uoyrararng) Esau “SOMENOR 2404 ogperea (ya wets (rhea ccs =x 90 X= A) on ge Jo ) 0 4+ HHA ‘ogo oo ems a = mt as # 77 ssono sonato taponas an 32 = (2)(22) 7 aay Pp Ue) bp) UIs xm] =x ER =¥ wO= x MY OSB Hx =X PT ‘womenioysen amon 9 280 Sayom sae vonenbe sa8uIpaag ay anor Ares om oaNPLTY on soy 1 azyy x09 fo 82} 2p Guo soy epoused ay ange pot 29 01 5S 1109 Jouerounp-2uo oy usond0g 10 sm as Yo paso 2onid a fo 2,00 245 vo puadep sou op sowiodoud aqqousosgo omen ve 128 om omens Exp Bunransqns Wo (2) ‘ectew assep om no Sark ps wwe (2h) mya ‘2x8 oy pauyquio oq eu (6) pos (5) suonentig {uo toga wans) 19 y 2-= w qu YP = ug = Boy (eo) us ya 9 vans 2g wonouny anew 999 = @ 205 “uo zaqumu ppo) 6g = w a= x = ak (em) 9009 =A 4 want oq ny wonouny anew a9 = Y 30 5 Ue U1 A = 2m 20 0.= a ag a4 na 3p) “be °C 'T = 4 Mu = 220 209 = y so oye nts 3m“) a0 soy pu asc reomtya fo your, ¥ 7S4 A Textbook of Physical Chemistry E=E+5,+E, 2) we have three separate equations tobe solved, each of them has & form of one-dimensional box. Thus, the normalized wave function ofa thee-dimensional box is J (1428) ‘The constants @,, @, and a, will be given by (1429) and thus the total energy is x Ba E+ B+ b= | (1430) ‘There are three quantum numbers, one each for every degre of freedom. S$ Example 1.43 The ground state transatonal energy of a particle in a one dimen length is about 4. Suppose thatthe sare particle is moving in )? an 7 42) 00 pm) Example 1.4.4 Solution Wave Mechanics, Enerey Quantization and Atomic Structure’ 5S ‘Theenezgy expression in a three dimensional box is =a = ((4 eV) (300 pm =4 x9 x3 eV = 108 eV ‘econ cd nnn! xg 18 is ound Say osetia Seana orate sou ‘ernst ny eden etc ot gus fe Cnty Tn cts egunace ae cette Strole stom Samer tse en ud Sten fewre seme en ceased Fanon tinea setae i Thu etn su con ic ison ot eg 0am get, Sn(O1é am) For the two-dimensional square box,01 x 2909 = x €209)/34 3000} _ (use ® oye yf 305 any 28 WU OL = 7208S 1x09 runs 201 #30 0 8p wo 8 OT 3p aanreradn »ss0sod fal 9 0 OE rae Joana Bea 291264 TH UA NS pauguon wage 3 008 a poy so» 10 ABs appt SHEaHY UL pee on x 4081 = ixyri=av ML Lovx vegeta ney i 3609s UF (@) fg 01 2C= a Migeay 20H 90N on e698 fue Hp OT XEEIIB = tu 4 fu 430 qt x 9299) (to g01 94.01% £099" Couey oF yaya 210 #0 @ 01 1'6=) doman we 9 TEN oem ggg = ssa aejot) wore voH a (e) 10) Ae t= Jp 8 Se Soma gambar io 3 2A 15. sumonns spuory pu voor «Sz2ug ‘SOMO PML uonnjos Le ordurexs: uonnios owt wens { gull X 9968 = (qu Ol XP ERIE AV SOU (Eg OL 7 ABE PL Azone J [OH HHL 01x p E8196 Abono yo [aot aesudop Ai an wos poem 29m pou 5 ms po 95 a a Spay pur "ou wos jp egy Bueooy ava ge ap 040 pena. aq WE uO022 Ue SUL, soy avs yw suan2e}2 ot fo woxmguaser va ‘agus wmsuont) “Pomoqoy ay Uy amoys oe sonay ABBUD may Vy Gust Gepep Mes sw a sso Aion oa, uate sp 30 ate pouoxa xy 2930} Jo onyea ogy ae] “Komp 0G oped yds 2p Bupdy suoney2 gy SUNOS uM Z'| BUN ap Jo x09 GND Y tum gg = uu ge x © y 1 YC) 99 pow \puapxem Fuppoodsauoo ap iau> oy uonrodoad Koss sua KeM 325015 ee atau? ~ lee av z=" "1 =u woy paounsd s|vonoap an uay pautngo sas paD wy ap 2ouay pi aves puss aq x perdnono Agnop aq sexs Alsou camp 835 uonnjos srr odwexg Auspuoyg pwortyy fo yooqe), ¥ 9S58 A Textbook of Physical Chemistry Now the average kinetic energy at 300 K is F-3 w(t lr=3 (aes sot m2 sane }eOe =62u17 «1 Buaing the above enery (8.263 x 10" 1.5 QUANTIZATION OF VIBRATIONAL ENERGY Harmonic Oscillator Fig. 154 Chasiial treatment of harmonic Classical Treatment Avr Stwthed Compress Nowton's second law of motion, according o Which, we have Foor e Eguating Egs (1.51) and (15.2), we get ‘mechanics, the above vibrational motion can be described in terms of (asa) (153) Classical Frequency of selllation Potential Energy of the Oscillator Fig 152 The Patebolc potential ‘ergy forthe ‘harmonic oseilator Wave Mechanics, Energy Quantization and Atomic Siraiure 59 3) has a form (Use) (1540) “A's the maximum displacement ofthe vibration and vais the frequency of depends on the mass ofthe puticie andthe force constant of the ‘connecting these can be derived as ‘Evaluating the second differential of Bg, (15-4) and subs we get m= A Conve)? sin Onv¢)} = ~ heA sin ave!) or many) = ke -The potential energy of the particle at any instant can be evaluated frm the expression Fo—dViix, ie, aV=—Fae ‘Substituting F From Eq, (15.1), we have Va kxde which on integrating gives Javakef xox in Ve 356 ‘The variation in potential energy with he displacement xis shown in Fig. 152(Cur + uy =]0 seu poonpas fa peor s sor a ‘(no}ou oHHOTEP¥ a .@= 4 Oct ~ 2402+ ,K08r~ f9= the Koz + S091 ~ M0 = 5H =H t+ M6y-,01= "H I= 4 ‘emiouned SyUNOH med TSNaOHL FST AIL aq wang 9} worssanda sup uy oquUGS aL 7. = & orp («fou (282) oyssanxa 19 4a a (651) bao stooge Forges moe Lt ‘ore Bupryou Sones esau Au aney ues YoY JoquM 4 pur soso tp yo Kouonbayjotsep ap 1H ata oh Coa) tay (Eon) =t9 aly wysand 2) vn fp pope eno om BHO “I are synser yeuy ou, edey> atp yo pus ox ve I] axmxouEY ut poquiosap si pox; oe) ape perp ste Zouod ay sone i 30 UORMoS SUL 4 A( 242-4) gh (os o=a( n'a) get dp fa sans uonou ony dus Sumoore nse apy uopane BUPANPS crest Jo omn00 dy Baunp vonsod wpa on ura app sony 220 ZRnuet pus jm anand ou xp pasado st "wowea o souany® Spe oe pe teu 9 = + JNO 30 DORA 9 20 peo ano Sop 20 oe ina anu Sy = pao une fees ate) = TY 19 einjonas sauory pun wossatuond (Baouy “somuoy>oqy 24044 {amon dop a ens ov ye ous ot Ser soz enoaOd poe Zhan jo uns ap oN solo G'S ep HRA ao pT ‘a0 {quo spuadap 2oyeqT!2s0 uv Jo Aaraua [EOI amp “zourS “esIAA soqA pure pusds "por 28 ope dan wae fo ‘vod Buspusdap s9p1soq “jpnmed 2 ‘$1 $1) amyeu uy omoqesed Jo |Biou9 enuanod Jo uoneuea ayy ‘sm. (6°61 bg) wowaae|dsp ap yo azenbs ‘3p uo spuadep ‘7 wo Burpuadap sopisoq‘sjoqued amp yo {Bou feNuaIod aU, « ‘Kouanbay ures ayy ya sreyH9s0 qT aJonNed op apmydare ayn 2q Keun soAarey 2 ay Uo You PUR w pu y uO dquo sonspanems fuuoyoy ancy jm wonow aquowsny ojduns Bunncons afonsed 94 @sp wrt=g 0 aaa)asyy'a © + np soy'y S= ug), us, ve + ee = OWD,U VG * —Gaagsoo Gave a iiaxgvusy) Eo oo Aeooue vy) 55 + eon SaravI] zm ie gt peat Atasa st vos 6 aan a9 Jo i090 SH sp (xpys09 Casigvu = Rw saw =d ” 40,e111980 OU sy yesur ue ve somed op yo umucwow qs, yo ABs0U3 FeIOL, suo oossyy fo yore, ¥ 0962 A Textbook of Physical Chemistry Depiction of Energies, Wave Fig. 153 The probability densities ot ‘harmonic oselator Quantum Characteristics Figue the: probabil Woe ston ‘A few important features shown in Fig. 1.5.3 may be highlighted here * The vibrational energies are quantized, and the separation between the successive energy levels is the same for all values of 0, i. BE=B,,-By= hv the classical picture where the particle has zero jum position, ie. at x = 0. xt = Hence the wave leven fora large value particle at some large lator which has a finite faclon yard the Cs and tan Gere tatu obs Ts {pith ate maybe dered a ‘ecto ang expeslnt as ies ck ta deate (ort) ing ie ae {Ous.Dhn ee a Problem 1.5.1 Solution Wave Mechanics, Energy Quantization and Atomic Structure 6 the probability of finding the particle i ton (the socalled equilibrium positior ‘Praline expectation value of kinetic energy of the harmonic oscillator inthe gro "The ground-state normalized wave function forte harmonic osiiation Is sine is wail ne expoctation ae of ite ere is ve by Hence (7) = [arcane 2 Fen a? Least} feral? |(pp pms 28) 7 o sagan | Ho waa ~ "* gaey on “Sm, ( x0 oie B)- cage Pp pon peeeunoy my, pan gp ip oSUD1FE out oon Jo Yong a HS PE ORIEN rsx por d uy sonumsoun avenbs weou eos 0 npend a mI aco a 3 aes pool nao; pe dx 30 sna voneHao 20 NEAL eee ua. sy somos squouney © 05 wonddng on8e ideal sos euie"s mL wihs Jame (hz 4 ras Wve Gh ais sayy ay ane a f= @e paDs a 205 20S MN 2 (Esa) alge AVG 1 soopsxdo sion yoivesam amaeb po ess Bebo oes cg apo ameao 99 yo wouerep WOME A a) aA vain apn =e api ee of sry rn 8 “nis sou 20) wma 8 pew 0= 9-189 = {esgn9 eo ar rH} (ap (ag )42(vop2) “aso 51x yo anges su en mons "2B sear tp yo woRDuny areas PATO IK ap YAH Tex JO SHR HH a 9. aon snuory puo wortrmuond) CLDUG 'SOMOONY 240K uonnios gg) wolgold uonnios: pst wereld tumuceesrqnx9 94 vorsuny a ‘24oqf 0 = 1 eae au st xP/A,P tam-)ar0 em +0 { 4). 2 wer) Me #248 rye ap /%,p 30 aye 2m woe a “JO WI a PN 138 9m (0 = P/°AP 99) we $= poe g =» son uopssaudho anoge ayy, (x0-)600 5 wopoon anna me puna ou, uonniog cumuew a SHO aioowny aio uopsong ane a pnoal am yo 30 ae 9 sua «SL. WGA trop ae Sty vn pu 2m XA) po) BtRAGD on = aaah (em +). yA SM) Ow YU) sp (410-80 ano uwopnjog 83 a4 pur om post on wr om%0 anon fo aq hneg ——«zS'4 WORM ¥ MAM 17a) yor" 1). } (we) =U) veh om 1/9 =0 poe yiouez =0 204 Kaaspuoyg porssyd fo x009RL ¥_ +966 A Textbook of Physical Chemistry chs Jvitware 2 freqearyar ve? fH [apey"} oe tate feds (= Jv(Ag)ve 2(2)(G)[evcwin [Lancer - (4) (Elo ‘Ponoe ar) ax <0 7 ip ES |ve (8) (Enon which is in agreement with the uncertainty principle Problom1.5.6 ‘hat the energy i given by eeth yh Baim” Bb (since the integrand is odd) Forte ial wavefunction y = a exp(-be) fora harmonic oscillator of mass, show ‘solution Problem 1.5.7 Wave Mechanics, Energy Quantization and Atomic Structure 67 ni wi eet a Stemi be pein re inane in gman we fn The Henn peter EB li? Brim de 2 emery ni Has 5 ma 1 fatipa) em sam 0) (SP ae “To determine minimum energy, we set E/0b = 0, hich gives hfe ee fh mae no Vm a Vm “te expen of romain of wave nto i Jvtee=t ie @ femart = (3) =I ere TS Tho eigenen forthe second excited mate of x harmonic ce Haw tyt D2 Aaa 2 = 200? mo. miiiin dem fig. 4 and an me, miHin ra a yp Meon ee ony 2m am weemtog 4 98D a Jo st w ama 99 Bo 7 BMT JO TUOUON aL wR ‘WORSE Aq "uarsKs m9 Jo epuoU! Jo WMO amp tj SION won wee +hiny? 5 gotta? « gotnta® = MOT = forty + olny =a § atmo} 2x4 3 22 5 poe poe esos (on tnt Z intw Z T cet 2m J ABtoua oneury ayy “sxe mp pow Zueor Te Stem On apo soniaojan oxaadsay 2 94 40 PUY So¥0 so 327 “ojnaajour ap Jo swore om sy waDMq 1u ¥ yBnonp porouu0d are (swore O38 Fue put sasseu ony a 9204s JOH pxBu JO ‘mmowep jo wonouruoneior ap Fan aA, S31N9F7IOW oworvia JO AOUSNS TWNOLLVLOY 40 NOUVZUNYAD St puowneeld eaisseid B eemontis ery pre woreemongs ” ee ee ee 292-795) = » F204 Fon] = yew gm) a ny weed 200) (5) asa vores nay 51201950 mown xp 30 oreE4o ee WON SUL, Sita = 8 wassado ayia yoy EAD 6 ‘YORAM UE SFA BS (@) (tee euro PLO Leo} om 30 puo am We TT AmE=UOY 2S "woneagsaen ot 04 Sade 2 Jo 9 2 AACA 925 | 79) onatt rors 22 22 (88 ae 1 Va spre «(Fe ar-a{ ozo ‘2 mp Sikes ax 309 uyssxdxa Humpundsauoo ayy, 79quin REND a tf = z91) IM + OF= eT “Ze snes perrvenb 24) 405 vowssandxa Bovxonoy ap septaoxd (229°) bao HoAMos 24 Aa=A7 Jog ouay“qumytion 2 o ams J smsad0 yo obs yor a uo voresodo op “Soxoaiou pu a= r9'1) bao BpI0008 HON Seas (28 jeer] eo) suso=4| iia eioes euata rag se oman 29 sm (6191) wouenb pu g sempr00o sip wo ‘Yoo spuadep yon sruowEy auyds se unot (6 0) wor2ary 8 KqpoDea! vo SYA wonoUN a 80.0.0 (#8 jee] se Crs Oour=@ ou [REP 5 (Lous @ ous =¢ 1 | Be -(o ert 64 am 01 songs 191) ba ‘Seq “(GU'9°T) “bal UF swede ou Ym 4 o1 aOdsaH IN aATEALED }}s009 SuTEay 2OyEO! oep Jo SOESEUL Ox ANY UHNIDg SOUEIIP 2p AUIS Ag=Al +( Som] 2220s" (2 ee 18 ear Oneal every a _oj9q uonf st uorssaudx pamoyseen a4, 0 6 203, et Kasspuoyy poorssya fo .oaret VTTA A Textbook of Physical Chemistry Normalization of f Ain Eq, (1.632) can be det normalizing the function ad Eq. (1.6.32) can be determined by normalizing the function 3 24th fetes doe oc FAP Qe) =1 L or Ae Vie ‘Thus, the solution of Ba, (1.63) 1 m= Foe eaplimipl: m=O. 2122, (1.636) A few tormalized 4, functions ite given in Table 1.61 ‘Table 1.6.1 A Fow Normalized @, Functions =_ o wie “ fax)exptigy t Lia) igh = " Lia) exp 29) — Expression ofthe Solution of Equation (1.629) can be writen ina more familiar form by defi Normalized @ Eq. (1.6.29) E=cos @ familiar form by defining a variable Ths not @ @ With the above relations, Bq (1.6.29) modifies to 7 1-€) #| +0. Dividing by (1~£2)P and rearcanging, we get 4a al, Problem 1.6.1 a [t-egh fern atesle# at oe 0-8 Faw Es [ra en tglreo Wave Mechanic, Energy Quantization and Atomic Sircture 15 ion (1.637) is a di equation called ion. The solution of Eq (1.6.37) has been dev associated Legendre Sees, each of which must be restricted toa finite um is to emain ite everywhere, This condition ultimately leads tothe requirement 720123 (1638) ‘The solution Pare the associated Legendre polynomials Pj of degre J and ordet vw and are given by the relation fl papitaa- ne 4 py 0.6.39) were Fis the Legendre pom whose form depends only onintges J and is given by a “a5 ee! (160) hea ae Ee tive imeges the solution P of he function @ aso sequies This follows immediately from ome zo if mis greater tan (Gq, 1538) ma,222 430% sab Hence, m can have (J + 1) values for a given value of J [Now the functions @{) ae identical to the solutions of the associated Legendre ae ee oy L439) Hover be ants ghey (639) Sr mando oon Eq (1839) duth be eso jeresnouen. Py (16.42) J The function depends on the values of two quantum numbers J and ini. The or the given values of J and iml can be determined from 39) and (1.6.40. determined from Eqs (1.642), (1.639) and L640) for J=2 and m= 0. Determine the frm of the fu ‘The O function as given by Ba fax2ey 2 10: Ou” i2 jo wossands Jo woneyap am 05 JENS a Jo Pua a AINEBIUY 5S font} aie {awnte)y ean 1 2 pow 7 somado ayo seen -anlyp up Busaprsuon Aa, pouruunap 99 oste Ue w pif UaamTR9 WORE aU, jposjsadsun fjreydunoo si of akp se opd}outd AaurE29UN amp ATION YU SHOP Sra Pomoe am (she-2 ap IPA mrBvOWOW zejaFu ap Jo.g effuM UoREITOHO ‘ui 91) unnomoM zIN8ue Jo wuodu: ongen 29014 2p ‘St, "2 1&9 ame w jo sanqea panned a2 ‘(py9°T) ‘ba 01 Bmpuoaoy wurqNawoU siuaaidas yumsu0o 07 "243H pe op Jo wnodaion 9 Jo wowezmtenb (rot, @«a a yo wovoduca? ap asym nyo onan be surat 991) ES oven {owane} Sue ‘ [ono BE) 8 2 «feu 2} 9 ‘ane am ‘Sm oe we _, oro) eae yd ‘oy aip sey woreks aeuspions pearouds uy soesedo ayy, wrnoxost sninBue Jo uauodutos-z yo zoyes2d0 ayy £q pasado aq (dundxo (ezh/) ‘uonouny ap aya yersuoo ao soueaQTURT PysAyd ep PHBIIOPIN C10 UI anes asjoud anny mea 7 turasowous seeue ‘eo wosaud 2 Wf “ee so ajen sey 58 Tom $07] Wry 20] OsP7 Sf JON poe LUMI SA, 128 mu 18 ca ppetbeg rg oy enna ous Alou 30 ‘uoneznuee sip smasaidar osye yessuoo sty "woIKs ox jo wrnaEN ENTE Je uojeztmenb 24) 30} spun Yor Joquanu targsenb sip St oRwOD om ‘mE, LL. 9imiomas spuory pu worgruond) Cuong ‘snumy9py 084 w puep sjueysu0g ouy uuoomjog uoH tw queysu09 ‘yp yo coueaytuBis eotshua a »(zp) —— 7% aw) atnih=7 0 * Gerara a ‘2n J0 s2ueo4UB ‘anny ant *(€7'9'T) ‘by WoL] ia = z z z 1 ° 1 ° “ 7 Ssuoqoung "9 pazTewwon mag y 79°F O19 suonoung ‘suonauny 9909 Jo tos sopayout 79" a|qR."POUTHE=. 39 pUE JO SONA ‘9 mod WaR_BEP WHA SvoNDURY IND OW [9] Wojgoxg UE UOAEe pog>M ap SuKOHIO] Jo Suo|Ssada ( 2) G- $07) ¥ 0% a-om9 2-9 oF tum in gsosn}' omg Oso aR Uxth) _(Z_ 42) (2) 0 ED) -(e) re 4 vont 51 (6E91) ba way ig 2) ustuoys word oyoogeas ¥ 918 A Textbook of Physical Chemistry ts Ef Fewine| = ie fn 2 ee xine} =e(Z) {even} asa that is, the square ofthe -component of angular momentum i (m2), Since the angular momentum isa vector quantity, we can write This coaition wll be fulfilled provided ln < J ‘Ts, the values of mare restricted t0 m= 0, 1, = 2, (21+ 1 values. degenerate (Le. they have the same energy) asthe energy ofthe sy ‘only on the quantum number J. Since m is confined to fora given value of J, vector of magnitude 7 crete values J, J ~ D, that te orientations of the ang pve Is such that its component along. the axis can have values of m(i/2n), where m can take any value out of J, J~1, *~, ~~ 1), ~J The angular momentum being a vector quantity can be shown by an arrow whose length i proportional tothe magnitude of the angular In Fig. 1.63, the orientations of angular momentum vector labelled as ae in the plane of paper. For m not equal to zero the angular momentum vector ccan also point out of the plane of paper making the same angle 0 with the ‘axis. These orientations are shown under the label ‘Thus, any vector fon the conical surfaces will have a value of J2(k/2n) for the total angular Wave Mechanics, Energy Quantization and Atomic Structure 79 ‘momnentum and + (2) for the z-component of angular momentum. The fact that ‘uncertainty principle (angle @ has a precise valve but not the angle g) In her words, the quantities 1? and L, have recite values but not Zand," Pa mg eon o © ® Po 4. acc an L63. Possible orientations of angular ‘momentum vectorsfor «i, (2) exp tig. the end ofthe chapter fr quantum mechanical explanation,roneurydee 29 sud a0 pus DLA HMMBNLY 295 ‘anna sip te snowsgo S11 ‘worse pue snofonu *ffoueu “soponNed OM) UES sais o-tonphy ap ours "WALKS os ap 35} BoNDANY ane at Dv Aéroua onstaneamvon fon sp sty ‘woresedo uetuonumey mst py 28a ‘oq Poysuowp-2anp uy apqued ain Jo wp se WHO} uuopen ‘ams ap Jos seu Jo avo ay Jo wonour an saquosop y>RHM (pT) woEnbg wen reggae Eacncea ‘bg Bajos Aq poupigo 9q uno sofuoup ortomc2p 0 Sone pamoT 2 Ss wonenbo 18upanjog 30 uno} wapuodapur-simN a, yo Bumeg 2 Sutpuodsonon 2p st 9 pue A wonouny 2&9 Jo moe a, Jo SOURIS & 1 Z IN 2: ‘swoie uonseo-Aueu 0} “fen areumroxdde ‘m) purcr® Buajonat 5} rf SEO paonpas Jo wonDdye ow © vr ‘pordde 9q uvo toon sup Jo so[dionad am Moy HOGS 29 TI tn wnsks og suorards yore onenbo 292uNpon9s ot 3 ar aonaas menbosqns 2p wen wanDsfe-ou0 0} ay sae 5 J98uIpON>S Jo uoneayéde ap soptsuon oa ‘uono9s sO] “sone xo ason yo ezzeds pue ‘ory sotfiova quons29 Jo woneznusnb axp 0 poy leoyp SH TEN I Uo9s ‘Aiooun [ucoay (20. pe} es8 sem 3 ‘vona9p9 9m) Jo uaoaGom ZEST TENGAO Jo uONezNUENb Jo uonduMST — s..YyoR BueIde cen ‘Ag =A fF a ete all ae J syseq amp uo paseq sex Atoom s,moR aqp Jo WoMaUTeL] TeoNeMaqTEM sy, Jo Asseoon WOLY NADOUOAH SH ‘ADYANA SINOMLOZTA JO NOLWZUNWND Zt (Be, Me, ey Cus") ue wen “0nn (1+ Dz 2 “euvign(@) 5 anresuads oy, werulo- | orm ga) 1009, 9 >) ‘ame suonent aa, ore ap un SNAFU aM oF ads IL WoRDd]> AHN JO YON ‘agp Suaqonur zupo ayy pu 22eds m owe ap Jo sss Jo aU tn JO ‘ay an Smagoaty suo “Suonenba scams om on u2yO39 94 HO (E 300-18 2-1) 9509 +9 5009.08 P=} {gs00—g2 500 9500 + @z uisz-J9 US] 208% + ge soog my 2A [rot Gz 99 ws) | Feet tig 2 82" (ree 9? guy) 9 U8] AH [»s ss ome ee ~ y= ‘sn, “snopoau axp 295 340 puR wen - (omen on fom) wr009 sy "214 “sue om 0} sr soreump000, ‘won29qo am 39) 201 yer a,“ : 09“ 10} aan pe (2 "4 2) jqezea ayeurpr00o xs om uo spuadep "4, wonDuny 1g Panos apuony pu woponsuand; KB. “ouny209y 260), Aasuoye powtid fo Yo42eL VOB82. A Textbook of Physical Chemistry ‘The solution of Schrsinger a the uation i exprecced inthe coordinate system that celeste symmeity of te system. the present case the potential energy fi form the Schrddinger equation (E spherical polar coordinates 7, @and 9 (Pig. 1.6.2) by using the re V) is a lengthy and tedious process, and only ven below, Faf2(r2) ated (med) shee Setar ar” ar) sin da 30) Stooge | ~ where is ftion ofr Bad @ Rear ing the above expres fa n, we get (r 3) aealeed) oe zy Equation 1a snot 56) Since the operator is made up of two terms, one depending on the variable rand the other on the variables @and p taken together, we caa Write the Wave function 145 the product of two functions—one depending on rand the other on Gand @. Hence, we ean aan ataagtere ae Wave Mechanics, Energy Quantization and Atomic Structure 83 Dividing throughout by R, Yo,» We get roma 1 ~- [Ee a@3) aes}| eed lds good only when both sides are equal to @ 5 '9) separates into two equations, one depending only on 7 andthe other on @ and g. These are Equation involving the variable r (« 2. Gre) ) ‘Multiplying Ba (1.7.11) by sin?@ and rearranging the resultant expression, we get sa se Since the operat two terms, one depending on 0 and the other on p, We can write the wave function Ya g 35, Yag= %% With this, Eq (1.7.12) becomes a 40; ) eo Ce sino “(sino $8) « 1041) sn? 0, 0,+ 0, 20, =0 psn lina) e109 a Dividing throughout by @j@ and rearranging, we get ao, 8 (igo Barer nsw'oe 12% any os a5 ap a ‘The two sides of Eq, (1.7.12) must be equal to a constant, say m?, Thus, we have sind d 49, ) % 2 5 (sno 82), 104 1 sito an Sw nO) wi 128.7 @, ag"soy aqui aay wos Psa! 2 sms naod sp wy sanbas uonipco sue] a ds Ysa pn pe BoR=NTY ween ocen ‘quan st pun °F spo pur (7) 2289p Jo aunty xy spoon S08 od a) Ka pauaep S "10 oon» A Bey(°auy) en ZAC Fae ee rest ore) reel un wo=d 4 van am pd su >, T ye9 = 8 = Ut ouayos ommuojsoen Buon YY 7 UORSUN oy mass y Mono HH @ren (1 w= uw ‘wowonba auioniiry my asou Burmojtoy om (OT patoyoosso se 0} aIqyssod pu oz ‘29 oxy pur ajgeus wepusdopur Jo von 2D wonenbo a ono arenbs 2p JO woneznuenb ayn siuasandat put 38 9 30 sequuna wnguonb pyran 2 91 be Be eat ta) ‘patjsnes ae suompuod Busoroy ap poprscid poureig ax Suproooe wmuowow junu wurygenb amgaenb of, te onw 8 amma sruory pu wo neon «Buaue “orucysayt 240, uonenba quapuadea-+ ye suonnies ue unjod aipuo807 pareyoossy (as ba) 35 ay -aashs somes Panos 92g ose sey (p11) vonenba (xcs) uoyssexa a4p Aq vont axe uae sous wravamow infu 2p Jo weuoduoo- ai 30 uorezitenb yy suasanday y pu sagumy umonb onauBow avy pays =} wi wEIsUOD ayy (eo bg) 4 Guo Busyouny wononty 6 8 guys) O_O. ep °) > aus (rer ta) (ort ba) 40 uajous uonondey ‘suonenbo 2m ou porezedas wenbs soBujpanyos ayn “sn, 226: ayy jo suoyssaudxa wonenb3 qwopusdea-9 Jo suonnjos uonenb3, ROS ids ony anyon porstyg fo yoognas ¥ ve86. A Textbook of Physical Chemistry Allowed Values of id its Relation 1 Expressions forthe Function R,,, n restriction leads to the fact that 2 which is equal to k~ (Eq 17.21) 0 bean intger Let & be wien as 0 hat. bene! 72 ‘Thus, te fanction R a given by Bq, (1.7.18) i Raper pst (72 Normalizing the shove solution through th expession Jar Parst 22) (n-t- west Re er pst et {z) Z per ay 1.7.25) whee p= 1.730) and ay ars ‘anne? The constant mis refered to asthe principal quantum number. If the associated Laguerre polynomial (Eq, 1.7.24) is not to vanish, we must have isk 173) Since j= 21+ 1 and k= n+ 1, we have (1.733) ‘obvious thatthe principal 4qvanturn number cannot have @ zero value, The allowed values of m are only Positive integers, Thus, we have 21,234, 0 $201.23, c= D 734) ‘The exact form ofthe function R,(7) for the given values of mand I can be These equations are (4, 1.729) Es. (1.724) Problem 1.7.1 Solution Some of the Dependent Solutions Wave Mechanics, Energy Quantization and Atomic Structure 87 ant ty nt Ee ted wn} 4 1.725) Determine the form of function forthe values of n= 2 and I= 0, Substiuting the given values of n and! in Eg (1.725), we get --{(22)_o-0-01 | {z) were Las given by Bg, (1.724 where Fas given by Ea @ pe nae een [Now working in the reverse direction, we hove 4 [6 rerlerd -04 {4 gerard oper. per a ed (bw i ap ele =P QE 2H IPEP + FEF) =Q-49+ A) 4,04 ye bye Lenape pane 29 Ban Gat age ee 2z),_ (2) Final, since p= {22 r= (2), we have ame o-()- (3) ‘other functions with different values udes some such functions. Problem 1 Following the method given ‘of mand I can be determined.soacomp mad ov ou pu st a8 oy wanZHe 2 J 7 2 Jo savy 29 0 Ad Speedy uo a pmo a "oo sete ina meh 205 Pr] oe FE won2ayo aut 30 INO. m7 wanytp 29009 pe soesagp anny 284 Se UNO SEY. “A wonotng ane OI 2 ‘SM, WOAATE dun jo uonngnspseindue ap 2418 ayo way PHEE) SHOROUT Om IML su yo anen om so pdop suonny asouL, otfue Jo woman ¥ se wonnqutp ap aqk5sop foxy xojzan af vo Kuo puadop > SUONDA AL, & sa yo apnsnuew 2xp Yo Ko puedap suon aun} 6 2 't fd ayy nou, pu 71 STAqUIND twnywenb ov vodn puedop cong 9 aquoeap a ‘axojatan'9 Bue wo uo puadap@ SUCH) AHL, & suru 3 1UBIABHP ANY 2A cau wnpuonb poysnurey “aoqui mquonb podndg 18 om (EZUT) ba woHg (ECL) PH 7g uso poutego 2g ues unnsaf2amp Jo ABtaue Jo Sonne pawoMT OU, won puadap suonsuny asa, "SEN se ayy auonn faey w0 A pu SEH MAL « Sa oy aa rogue ene uy a3 ead stone Sb, "pennants Ae cae enb umazs supa Apo a TA ARIS PE PORES , (coc) orp ea) oe) oy “yom ‘ony a7e SUOTOUR 9 yy suomeanojsuen ajqeins £4. o> var eat) eed ea) zoe peo 'y soon 2 30} PO rep eng aoe ap v0 Snel 0 BOND Y HONS to juooounr poegatfue aA so ano eo AL oun jon 2) (8) 6 , eons GE Wt) ah 2) OPE © 7A um on 2} svopeaio gang ova sys wonenba J9BHPONS AL ¢ soreupsoa9 od fauowes 24 Ont ose oe sso oun oi Sujonaeonnbs PANS AL, « ay poe wonoo a go soonaan 2828 . xn Jo seeups00> (erura-yna{ ee seo 2020 300 uogenb spans si SPUpIO? yo anuzo 2m 3 sarepu069 a Uo spuadp 5A ray rn a a Maa se von 51h Vonoury 319 cwonoye ay 305 30mm pu smafonu a Jo seTEUIPIOND sony “2a “sojqpuen yeopuedaput 318 2ip vo spadap YH xh BONNE & at am fons ir sa205pK4 ap Jo ae EOE IMA 2 aQHOAP CL, soroods on-ueBouphe ou yo waueou jeoqueyoeNy umuEND oun 40 ENS ‘suonouna*y PaMIeWION Mog Y LE 91GEL «6¢_aumung oruory put wos KBs SHUNT 280A, uon291a, (9up 4o AB003, nruoye rome fe OO ¥ 8B90. A Textbook of Physical Chemistry The physic sintcane of quantum nubs, and m ae a8 flows pl quam umber describes the energy of the elecoon specie andi given by the celation Audet) Af 22 | oat [eae ag where ay = (Ane) (b) The azimuthal quantum number describes the total angular momentum, of the electron through the expression" Iris customary to designate the vals of by ets a given below valet OTS om os p a f g oh dnd fae derived from the spectroscopic terms hap, lite, ad fundamental respective . electron depends only on the value of n and not at all on 1 ith the same value of n but ice. they have the same energy 2). Thus, the degeneracy of orbitals for given value of is equal Table 1.7.2 Energies ot Orbital in a Hydrogen-lke Species axtuztet 7 anc rE D ee afi) mast 3 [arg 3 "rcan be noted ht forall states fn which 1=0, te fo lls ei, he oil angular momentum is ae value isis ot possible in the Bole’ tecry). The exbital mation of ‘he elecon in oils without angela momentum is dificult 0 visualize in classical terms. Wave Mechanics, Energy Quantization and Atom ‘obtained when the eleetron is transferred from one wave to another wave function. A more rigorous quantum- of “The spectra of atoms selection rules, For hydrogenlike species, we ave tl ‘nay change by an integer, ie, An=any value 1 must change by #1, ie Atl and mmay change by 1 or not at =O, ic. the transition 1s & 2p is allowed, ine I itmust go ftom a state of f= “The transition Is « 2s where A= Oi forbidden in the hydrogen atom are shown in Fig. 1.7. ‘few abe possible anit seston own. sie degauns Enna ronan agra. Te ie scr of Seton specu Pas emien copings died in Anesire IX atthe end of ths Cape = 188 e0r! Fig. 17 The allowed transitions of the hydrogen atom1 soups aed ous 4p wopssdo 249 ‘soupuadap seus apna ou Soop uonUN) anzm wats 3m 308s Soup) wee Ey st oetado WeDOHNH >, uonnios 1p mgs pur © 01 todsan yan 3 STUY ee) ) . me en ER) oat smu Path Mee Ly ¢ wt Fe Be nay se (eB hae sous a mp nous 38a uO Hy (10 Ho =A uoRoUNJ am Te sso] ELE AIAN 0 Song, 930 wo.saude uaa am _ ANH Baty mea sat (2 oy sant yor 2219 = opyap ws 980 01 pasos qn Bo 30 {zt He 1 wasp oops 205 soysodo wonnios (2) ‘is uno 2 nse py pr» wena} aor a pale ae ga __ tem May mtb [err — cog oe dtiad ° aa a umere sean oh ase arom ep tu) =} a opt ers wojaerg 6 aumzonars opwory pu uomennuonE Sty JO BoUEISIP ayqeqosd ISOU FH SEINE) LLL weed au "e a oa SS eee (te zy %" se mel npn fe a ee 2 (P= EYE ae (Eel orornens pee aoe ec) sae i Jel gm Dyn toot cat, uonnies rh a ce aches weal ene vomentroom san Sh. egal sons panos spo ea font 9 EH HON VMN oe i P _ tof ov om | oops (Fz) = (ove) (=) . 30 ONL reek eof enon] noc} (2) oon % 30 md [=z 16. among spwosy pun uoww2snaond Kaew “O}MOYDO 240) xsqucyg porsiud fo yoomrrey ¥ 96 ean thpopa ws uP 4 = 2p mS98 A Textbook of Physical Chemistry Wave Mechanics, Energy Quantization and Atomic Structure 99 Ele - Haier] 20 = 0082 For rag=3 + 03 = 5236.0 have Fe Heenan = Larais,i0.47240.00532) 20.191 1.8 PICTORIAL REPRESENTATIONS OF WAVE FUNCTIONS AND PROBABILITY DENSITY DISTRIBUTIONS FOR HYDROGEN-LIKE SPECIES {z (@) ZG) Tis espeton sere a Expression of ‘The various wav finson forthe hydrogen species are written a8 (x) ft Jefe) 2) -d£)es[ 2-2) <0 fave Function 2 ()-)1g w Vain RiPa a The 0s ate where the functions Ry, Ojq and Oy describe the r, @ and ¢ dependences, ot ang £0 SE E= respectively. The funtion R depends on antum numbers, and 10 also aiieeate depends on two quantum numbers, and lm and the function @ depends only on one quantum number m. The two functions nd @, taken together describe the angular dependence of the wave function, A few R, @ and ® functions have already been given in Tables 1.71, 1.6.2 and 1.6.1, respectively. At the very outset, A Hog 2, we have ade inthe wave funtion Ry Ter are wo main inte dit of A eras rat r= (3 VSlayand (3+ Jay, respectively Thera isbn fston forthe spec shel sted ata distance rfom te {wo iporaa enue may be rime oa These ae, ee we have - lues of n but the same values of { and m is (A\"es- ra] 2. The angular pu ofthe wave fancon fran scr is const (9! 2%) omy | with no @ and g dependence for all values of m. Ths, the functions i» Wa ae Yon (ors 5.25, «als depen ony on anda spy eg) (ar a syameticl Bap a) a5) lots of Functions Since for otils Forth ticks oye hve oterype ; 0.0% Rro 1.8.1) tooo Fe asy rag} For rlag=3~ V5 = 0.764, we have The plots of Yano versus F will have the same form a5 those of R versus r. 1 F = 5 (0.7647 (2-0.768)'e2™ET wage NeSBROR Aa 296 “Ep 2— ‘g0 * pe iqpgond a smous zg°1 amg “A on penbo Any spy A ou a4fonut ont emp Tt — £4 1 Sureqdos &q paupego st yor A Jo aesnf09 ord om st alas YA se vont st Amiqegord ay, ‘seapsaiag suon UT 31130 ot oy ue yfurueososou ave Aaigegod jo o{d mp “KrsTUONP Uy pus Be JO SIOIK ‘uo sou omy ox samo sjuanaye an Jo wom du05ap ans ore » ov enbe sty uonoury rp 2 ut sme yopou yo aqui ay wpa ESTA “mod yopou ay St wo 5 anf ose soy BoNSUNY ap ays Od au, “Jo nye s¥jponred avo ve ann fore %4 z= r whe :4 yo sonpen ose] soy ond sonpfoust GA p< 2 Z ® - Jo Fone yous 30} 20 ansssod | AZ > Z 681 Sta uy unoys ae saumotd uonstedod-0p up a Aq mONTD0] WA pared se Sos asou! Sas03109p 4010 Tenuauedx9 Supoodsan0 a JO oda a (veng “Mx2 @ojzz ~Z) wu ‘np, ,°2TZ) EY MSH. sD ‘fdas S00 A BONA Sa sunt. Sora wnpdalonpoogic una aeseoenA,Ajosets oma sem, wonendoged paveng m4 a 2 mony Demeter psc Br wy vw ® “1a pov (9 suorany woe ret te Bos sofont ap pune > 28 appar as eae ap SuOHOU 3925 U1 30 onoany sey pur y sonoury Jo mo4dyeuosuanmp-ows ip smoys Tg Tay My pue *y 40 s1o1g aamtonaig snuory pup uorsuond) KBs0us ‘sonoNDeyy 2044 Aaseraayg pe (yg fo yooqn2s ¥ 001102 A Textbook of Physical Chemistry Equal-Probability Contour Diagrams. Fig. 184 90% probability contours for 1s and 2s orbitals Plots of Radia! Distribution’ Functions ‘we want 0 account over a very large distance from the nucieus, iy. Por Is and 2s orbitals, the 90% probability contours KL ‘Though the probabiliy of finding the eletron in nucleus the total amount of the dot population naximum nea the leus. In order to (182) Note: Stictly speaking, he charge within the = forea feria fore frat rand r+ di ven by egrations over Band yield nity, Hence, the + 37%dr + 3nd), Neglecting the terms and 2 orbitals Problem 1.8.1 Solution Wave Mechanics, Energy Quantization and Atomic Structure 103 For Is and 2s orbital, the radial disibution fuaction versus ria plots re shown in Fig. 185, Je OFF ak which the mas observed is equal to calculated from the Bi of orbit is partially explained by the quantum mects very existence of the precise orbit in an atom has no place in the quaatum mechanical treatment, What quantum mechanics says that the electron has some probability for the ln maximum which sited tte Ingest vale rhs he maximum eight and the others have smaller heights expression 19 zero Taking the rai oustant terms, we get 8 (3, S(8 ttim «af 22) =e ~ 22226 a}jo anes 2 nb YoEuy oN BABE Dw NH ee 8a naiy weensieg pavot sagen out UBM “SSL uy umogs se aueyd (eI jo ade ays a8 09 e-RIp 01009 "A -ssovopuadop jue pur fepes ap SunIgtog 3) OTA wary a 30 doo AP 2 aq noge LST Bh sump OH UL, jo sonano ayy Sunet02 &q pourengo 5 ace Fug m unos ost 5101 su, @ ure panord slog) sy» uno 29 uo otepsdep Be a TTY @ ° 69 2fue any pours ou so am 20 304d 001s nV ayBue omy puree au) 189" jnquo*d apse 04 pasos st yengpo sti "SBE fm jo and yn 3mp 2OUIS DO a0 anon 0d SO O11 AD ys awepI0N> Sentea sOUTA af 3 ae wOnaTy ap 30s SUL LET aqrounugs ate pus uf8uo 2p yBNonp $e Ses soap pur aud Tepow-ce ap 2noge wr aU ro ont a 3001 préong ssid PP%O woo = 30 048 UOIHSTP-ONL ovopuaiapg fun suas 0250 onsen} assy staptay ne HEI 8 09° mY 2S XD Ly pe gm E=W0 wep 4 & ae sonny ane == 8208 sor 2ansomug snuory pus womreyuong) , “one ane 1 uy sopou yo sqm op 30 (1 =~ H) eto HUD eHt 28H, quowow snouben ye wovodwog-2 quowoyy oneusent yo uoyssaidea eoqueyson winuend 8 am “(1'6'1) “ba MT (CoD) Pu (76 1) sha SunMmnsqng a) yeey se 90 yvonorssan oro gy, pd peS-aon ‘Sf wonoay9 ayp reqs 19RJ ay) o1 aap ST (Z'6'T) “ba UT UBIS onNeToU ou, wen (2)-- (neyo oruan22[2) (puoaos/suonnjoxal yo oquina) = se asst 90 oun at Supe 7 23 wonoape 249 Jo paods 249 39.4 ¥71 wane oy, Smpedjo nto ue UF ‘saoq[oy se pousep 29 ue ue Kup sp Jo wowow onauBeur aq, "NOMAD aN JO HOUT GO aK HM oterosse st oueu Kun 8 uonbasuo) 109 yBnaxA uaUND yo afussed ‘20 spuodseco woroojo ue Jo wonOw Tego xp “soIUEyooUs FOES UY Hoo atp 0 wonoos sso yo wore am ty pe 2um on Jad yoo ai uy Buen aL 3g $F IaH ae yet nay saradury om wou parejnyes oq wea youBeu2yp Jo mous apeueu ayy, Ho9 a9 Jo sued 9, ‘0 smonpuodted pay anoueu » seonpoxd 1 exp Yrs St aueu 2x9 Jo uoRUOHO ‘iy, Yeu ® ssonpoad suosuouup As8urpso Jor} 7 Hoo BUT SuINOG, WANN Y jsond 2mp “Uoseos sty 20 sno 398 am 6 Burkes pur quowoyy onouBeyi youorssaidx3 eotsse%9 ANSWION OUANOVW 3HL ONY WALNAWON UYINONY 6't Aasruy porshya fo yoorseay ¥ ZLLd A Textbook of Plysical Chemistry lectron in = L state Larmor Precession ‘of quantization of z-component ofthe angular momentum, s( 1e magnetic quantum number. The allowed values of mate 0, + the angle between the angular momentum vector and ing the ator ither in a magnetic field or in an electrical field. The isoction ofthe field is taken to be the z-anis. Since m can never be equal to RET), i foitows that 4, can never be equal 10 My i. the magnitude ofthe magnetic moment Vector ai its component can never have the same value, Tht in p Orbital Le Yigee = fis) See fans In the presence of a magnetic field, the magneric moment vector executes Larmor precession around the magnetic field. This is basically dye to the quanturn ‘mechanical restition thatthe magnetic moment vector (o te angular momentum vector) can never be aligned along the magnetic Geld. What happens is thatthe ‘magnetic moment experiences a couple force whic tends to align the vector along recon, Classically, this alignment is permitted but quantims mechasically possible. The only ater effect of this force is to rotate the magnetic ctor around the field direction, Keeping al the while its orientation angle ‘constant. Thus, the magnetic moment vector stats processing around the magnetic ‘eld. ray of Electron The permited values of m f Wave Mechanics, Energy Quantization and Atomic Structure %18 ‘The potental enerey V of an electron placed in a magnetic feld B is given by V=-Bu, Substituting the expression off, rom Eq, (1.910), we get V==B Gig 60s 8) which in view of Bg (19.7 becomes Ve~B {-sa KTH} 0s O= Bg {JIT cos 6 Making use of Ba. (199) we get V=B iy m te erergy ofthe electron in any paticlar oil gets modified “= B+ Bll asa where E, is the corresponding quantuin mechanical energy in the absence of « magnetic field. ‘obvious that the energy of s orbital remains the angular momentum of electron in s moment is also 2er0, ie. the mot ‘ot produce any magnetic dipole an field can take place interaction withthe external magnetic jtals are +1, 0 and -1. Hence the energy of (othe following values. electron in p onbtals gets modi Egaiy= Ext Bl » = Ea Ex = Ex Bly Hence the degeneracy of the three p orbitals are removed in the presence of a magnetic field (Fig. 1.93). (19.3) Magee Bee emoves the degeneracy with respect Ingen he presence of maga ae which are fivefold degenerate become to the quantum number m. Thus,-won2opp 2p J0 vonous eq aan Jory se iy se aop) 5 WOT? jo 2oyutds up aoj one onpudeosK® omy vey serdar stu, (PAY 2neuBeRy 4 sou ened ojo Buns am Jo uoneutexe op #0) souapl2 ueusned= ‘Ho poppe tog Sey (OTT) Ba Hz abe a, “IP Tees FH Jey ons #yumasouion seradue p30 wovodwos-r ax swasoudas 'w soquina uamuenb 2qp pur § surmusui0M indue ds a Jo apmmugow jer o swueserdas F zaquinu umuENb 2), "a pur j siaquinW wrauenb pug. jo 250% oF EUS KDA sy sioquiny asap JO eee coojus easy ou, “w pe sioqunu uraeab uds omy Aq paquosep 09 eo as per mesmo eet rao ay Jo wep 5 wnenon Be — Js amp Jo onqea 24, “sxP Uno SE HOGS Buus O} anp waUEWON HABE vvonoat uyuouoa ce opr f wmyowour anew yy Sunreut09 YORE AL wonema .. " eae rer gmnosrou mya xp Jo tego asodd0 vONDAND waxy TM >HI FO UGS oF BO ISUINUT UE Sey woso[o amp wey posodoud £76] Ut YooqUATHA, pue ITUspnop BuUUIMS BLIqUOSeG eae rey ana rows fa vooae of Jo aands aL wowon oneUb eau eae J eaeds ay UH sygeop Jo davEsED ap UM} 0 ps0 UT SHeqUINN KiMUEN ‘pray onacFou v Jo soueege a ut UaRO speoU ree 21p 205 ensods amy ur ponsesqo os sy auy o[Buls Jo peatsut 40 couapsxe on, su payed ‘unoys dg — s1 pue 8g > st 1 samo yoe9 oF pean Apps} SoU SuEU Jo SersUOD fyeraae “eUO 28 samadde yorys auy fenoods e “ey uy “poreqdiwo> axows aq or punoj sf wannzads ‘29 ‘odoasolonu woRnjosax YBny Zopun poUINIEYD st Yooyjo UEWIDDE OM LON nds o wonezpen eds. TOIT yooya uewooz snojewouy annseds a a Sdaodoo yeopssepouou © Kune St “smmeyseAy ease? 64 ageQHD.AP 100 sev ‘onpen aus Au sey uinjenion maBue weds ay ous "TOT T 3 “unoge ae os, gisod ave wnyuaurot see ens amp yo suOREIDUO ot THO ee 4 van ore umquowou yeue wds ap 30 stuouoduen > ‘oy ‘snug, “271 ~ pe Zit + ame yo sonyen powxuzed oxy “(Z/t) = 5 HAN (Bom) be) ars sy sosen cures safe ds a 3 apmnsE vor! fam Seng -7t o ange suo Au sey § Zoqum unyrend ds xp YR PERO] SEAL oI B= 9 Tat ‘270 Jo sonen pOwOT AHL worn gro snap =H 8 am (Cort) baw (Cor Pe LOL mages py soqeur anon mmuoeEoul soe mp STUN TRUE OH 88g ‘umoys ane aso, "qgssod are Md 51 pu > sy "4d st 2p “Soja uon 72s ax oy Brprozoe pe nasa axow ou st KoeseNaBep ‘pau Jo aouarand am uy Eq 2p se umouy “oopo smu, ploy onouBem v ut poor wey aun ovo MeN 230K asms='s 1 yds ote U8 Jo 5 (orn ore a cou nds ote ue Jo sony jenoads amp jo Sueu: wp paniasgo gR61 UF uEMS7, —_yoayEY UPWIODTZ yey ‘SLOads3 NVW33Z SNOTHONY ONY NVW33Z_O1"L Sue's Soyioua az ra Te sRHGIO waKos ray “Srigz— pue Srig— ‘0 “rig “Sra Jo sori is Spaanoodsar yeseu930pu0u ashes LLL aumonug wory pup woworsuend) Cou ‘sommseyy #0 Ah paen coe118 A Textbook of Physical Chem Potential Energy ofa Electron in a Magnetic Field Spectral ‘Transitions in the ‘Anomalous ‘Zeeman Effect in Bq, (1.10.6), we have 2a (5*D ‘whet iy isthe Bohr magneton. ‘The potential energy of the spinning electron inthe presence of a magnetic fed is given by V 2~BL-24geteaDfeos @ hich on making ake of Ey, (104) becomes 8 magnetic fel, the o E, + Bum + Buss, n, and 2Byym, is the potential energy , we have For 8 orbital Here m= 0. There EZ=E,+2Buym, ad since m, can have tvo values, +1/2 and modified values of energy For p orbitals. tire, we can have the following combinations m= 412 + Bly + Bulg = E, + 2By msn th= E,+ Bil Bulg = E, m= 402 y= E+ Bly m= I E,~ Big = Ey~ Bulg + Bi= B, ~ Bulg ~ Big = E, ~2Btlg lily ingrar and 2p ofhitals. which also exh Fig. 1.103 are the =0. The allowed ction rules ted in Seeion 1.7 with one additional rule of 1103 Split the allowed Tasos: No sean el, {p Magnet eld pony orbital a "Magnetic fed with ‘bial and spin ‘aitions ‘Table 1.10.1 The Allowed Electronic Transitions inthe Presence of a Magnetic Fieldane ymyqio dz pu sy waaay suonstEN Tesngads x ‘SOI aA0qe word is0sy lpnnns vated yo pow op uo nods 20 Se WNP AHL ami =A pte pug 1085 F opUPY L ue ~ pur zt ~ “TN “TE ae fet jo sonqes ponquuad on UE = 30H TIT =# poe T= 15H SPENO Bz Jd Pu pawns © go aoqasexd ayy uy omy otv} ds yygne 87 Jo ABou> OB “TL art ~= (gt) an = (gM saad ayy Bono amp J0 sarous yenusvod oh, Z Smut zit =# PEE O=1 SH (CGO 85 OF tba) Aquo uonou 1280 2889 pores ) von wena yoeg-ualosed ayes eRED APNE $8 UNE 8 SNF SAL 50 poosanbx2 24 469 Aro 2 som gf Sigs Kons a Sy a ‘we (ppm 7 Saquin tunyzenb tunyosuoM pS TOY We YONTe|a We ‘SMH, (ort t@ (si 1 Sunuds a Gorey ¥ : von an i 00 et peneu oft ume tue RDO on 4 Peep fremouiou sepsu fqn Jo wogoesai as 6 ec & Haas wo uaBoNAG a— Jo ydnag wqo-uds assay wos fo 0090 VOL122A Texthook of Physical Chemistry Table 1.102 Spectra Transitions in the Framework of Spin-Orbit Coupli outing Transition - Eneray ay 2-60 me aN = ae AN = (18) AY =# (18) ag Vy =+ HB Ags + (58) ty Alkali Metals te eeston i inthe # obi and thus J » V2 oe od this J" > 1/2, When th elestonccenis {he net higher p obi, the pemited values of J” are 30 and 172. The enegy Wave Mechanics, Energy Quantization and Atomic Structure 125 the J"= 12 state. Ths, 2 + J” = 12 are possible which ofthe electron in J’ = 3/2 state is differen two wansitions J”-= 3/2 J” = U2.0n the observed as the (wo closely spaced jen-Gerlach The exeimental demonstration foc th existence of te een is due iment Steen and Gerlach, They pasted a Ded tome theaugh 2 slong i Se osencous magnetic fed and found tha the Beam splissymmetscaly i ‘wo as shown in Fig. 1.105, ment no specific interactions between the om and the extemal magnetic field fora by the le electron ouside a closed shel. Th Hee - 285 ‘where g is equal © e/2m, in SI units 4441 MANY-ELECTRON ATOMS expression of ~The Hanitonin opetator fr clon in mayen SONS can be writen as Hamiltonian | Operator Ha= aay “The fr term represents the tol kinetic ner fall then elections, the ssen veraiteats tbe muclearsleeonic trac ins and the last erm represen he clectronie-electronic re Expression of The Scinger equation as usual canbe wten sf Schrédinger Hayy = BY t Equation where the fonction yis a function of 3 independent variables 2) aceurately ad one ity in solving te to salve Eq ads. The majoray 2985 “0g 2 g 91 wants oy fog Bua nav yoacd 10 1p yorugeo 2g komo pogo os fo ana i on 27h 0A wo hell apaHeal ~ oroudca a9 Ren fom wowed un au aqounrouddn pencyeg fo 2 ord 2 f snot) se pam 2 Seu yoy odor unin 3 uo pos! poe NONMRS =A 051 5 rum 9 a8 — sand Suyojo) ap Aq uaa are suon2uny woHnquisip eypes au 9 SANGO nap suon guns zeeuy a4ry J2Ne| =A, 71190 ‘1 anp st posn Sap} 38) 05 suonDUn} 8s "om UI SS cm 298104 op wonoofo puooes ayy 's-P-TA “puoaes 2p 203 aBrey>Jeojonu axpsod ap JO $ueoanns aannajjo we Wns! UOsI9}» sya Jo pro] aBsEYD aU amp WOE anu ‘ajdtaexas04 ‘981049 s89[ou7 angisod ap yo Bumuaax28 ennoaye amp Se uno st Teyy yunoooe OU Ox FE SILL rapuNEEd aygersnfpe omy se ways oq ‘ou 7 afieyp moron oxy ‘ei Bo AHN-UaBOIpAy ay wy opdusere 304 “soHouTET fatgesnfpe ay » Hugena0o um $1 YORU ade ap poxpoul[BUOHEHeS ap OL ayy Suyomosa oy "a2 O'6L ~ 51 anya yepuouradeo ou, AP SPL-= ABORE+ AY HROI~= 7 ‘oy pur Ao seo -=(Aegel-)8= "2 =. ‘sp ‘ouo oy pee ase poe Tw ypoq ‘awts punos3 ap ut wore oy aN JO tq Jo yea TeousunU 2H, noove+ aT ‘A wos 93413908) 200A wf Rat) aa aA HA yo 10W op suoneqarared eas asain ein Sumas (aay) We 121 z owen reuopeyen ou A wo suonegimiad owen lew se patopsuoo ame saa vorsyndax tuans9j9 ay Poa LoREgIMUed oy | UaHeCUMYOA AY, oyrau pouotous ay) 30 powsew wenoqomuod ap 2x9 Buto}os a poxosduut 2q ueo Sns09 ay YOAAMOH, "WoW 34) Ul suaN29[2 Jo anoEtON ‘aniemumd ayy wosaidar ou op pue axeuneoudde Aix asp snsay onoge ou ‘suon2o}9 Snouea jo 918.009 [enpIApU! ay) rnbo st B1ouo jen ou, sarods a-uaHaxpAy ay yo expo eons 2p Jo muy ay, "zona [wnpIAIpu ap Jo SqeURIOD ay 3 nebo o Joquonu 8 ony} asrucyy poistyg fo yooanay ¥- ye126 A Textbook of Physical Chemistry ‘onsistont Field Method 1), the Hamiltonian operstr H, the complete and correct operat nergy Ecan be written in terms of adjustable parameters, The bes. the values of adjustable parameters can be obtained by minimizing te Yalue of E, Le. which brings Has close as possible to the true energy ofthe system ‘This can be done by ive of E with respect to the adjustable 2 resultant expression to zero, Take, for exam Cred G “an ad = Jurnqyare [-222 22] by Now Je(- and eee ‘Thus, the approximate energy # becomes #22) (2) = 5.10 y= 5.70 (136 eV) =— 775 ev ito be compared with the experimental value of - 79.0 evt ‘The above procedure of solving the Schrsdinger the atom contains larger number of electrons. Anot 1, was suggested by Haritee in 1928 an method. I 04, we have ofthe system can be written asthe product of one- \ex2)9x3) ~ o4(n) {isthe wave function of the electron 1, and so on. These oneclectron ns can be any trial functions, Wave Mechanics, Energy Quantization and Atomic Structure ¥27 Vie.+ Vie,= Be, a atm Solving this equation, we get the improved wave function g, andthe corresponding energy E, the SCF-method. Suppose, we substituted in Eq aad the conesponding ener Ei. This process i repeated one by ove for all the lector and thus we ge the frstimproved wave functions and te comesponding ‘es imgroved ener ou Bf, Sima the eomsingroed wave factions fo al he are obtained one by one. We then again repeat the process third time, the second-improved g functions and thus ebain the tird-improved wave func and thid-improved energies, This ed unl tae mh emproved ‘wavefunctions agree within the limit with the (n 1) th-improved wavefunctions, ie. they become self-consistent. The energy of the atom is then given by ly a 8 pes and probability‘4p Jo arenbs ap xy stow! ‘vonnatnstp famgeqand sures au) osaxd2s pr "enoaiopy Tuatiannbar Aqnysnunstput 20 2g sopiso ofie UONDUNy anew ¥NNSUO Ue a 1 af 2h J TORDMOHT ODD AHJO now op apes ve A po od you om sip pue warsis 20 Tn age suon99[9 Oa 2p YEU) 12 2H WOH} SOTTO ST, (yeild =" 21 wonaap an 69% poe ‘ sr ayn eno wed ‘uanoaye ai Aq patdnooo st '6 atayi uonouny npond eapoue a SI pe y suonoop op aq poydmaoo ane fp 1d ou cord = vwonsoye-auo Jo 19nposd nog 288 T6121] ‘se sain uno oj, paw 1} stona0ny anes ‘apse dantam 9g stonoays om Suturea0> waishs © “Tiaionndd NOISMOXA INV 3HL GNY SNOULOSTS JO ALUTIGVHSINONUSION!SHL 2 5 zaqun winger aeueU p30 $2 ‘pe jequsea w fin fo fea Vani © svoneRy WoRngenstp Aaygegoxd amps tans d¢ > s¢ st {Bdoue jo 19pu0 Butseatou oxy “yoys uum PIN O ‘wooo a Ue 0481 st uomDo[oxg yo fBiouo ayy xd 4 Jo onyen 24 uo spuadap ose penqi0 jnoned Aue 30 SBrou2 ervoe Bu TEIGHO eM JO KBIoue 2p Suproap uy wevodun you! ap stu soqunw umguenb peda eqn 21 Jo uonEWaNO amp ose pus uno wows sejue om jo wauodwoo-7 a swasaadas w equim umyuERD S750 wonoope2ip Jo wmyuauou yx8ue [eer mp wasakdar equ wuMyENb 2, N WT. 4M som 2063 pasn joquass > oe ot ' 30084, -Bupnoy a ur ways away atop aap stasasdas u 13 yuenb san an £@ poreusisop 5 paurigo aq eo wonoaqe xp 30 round ay! vo Sv spradep KBrovo ‘o 0s pe ypue p ‘d's yoquiks ayy pens se Pmeusisop og Sew sprig snowea 2p smi, stoeds m-HeRosphy a UT UoND=.2 uonnies PIPE wojgoig suoquiny Aapruoyg,popstya Fo. yooapeL V#L130. A Textbook of Physical Chemistry Spin Wave Functions for a ‘Two- System Total Wave Function for a Two-Electron System resultant wave func should be equal othe square of ether ofthe functions yj, and yay. The tw su 1 1 =F Wat vad= FU + erred) (1123) 1 fed = Fe Va~ vad Fe (Oude PAO] (124 The subserips's' and ‘a’ stand for symmetric and antisymmetric, respectively, ‘The function y, remains symmetric on interchanging the two eleewons wheceas the function y, becomes ~¥, on interchanging the two electrons, another funtion writen as 8. Experi spin angular momentum of a system and ‘Thus, we cannot state that any particular electro has spin «(or B). Say, fo example, in the above system the two electrons have opposite spins, one is having a-spin {not known whether the electron 1. or electron 2) and the other is {B-spin. Thus, we cannot say tha the electron I has a spin and the electron 2 has a Pspin. It is equally probable that te electron 2 has a cespin and the electron 1 has a Bespin. A complete description of the electron can be described with the help of spin orbital which is simply the product of spatial and spn functions. Th an electon in p, can be writen as aor 8 depending upon the spin of the electron 26) 1 factype) + Fee) + a0) azn 1 SF fatnpea) - a2 2g) ‘The first thee functions are symmetric in nature and the last one is antisymmetric in nature. Thus, interchanging of to electrons reproduces the first thee Functions ‘while the fourth one reverse 0. ‘Aéceptable Wave Wave Mechanics, Energy Quantization and Atomic Structure 131 Now, when these fou spin functions are combined with the two spatial functions watons as showa below. par} (symmetic) B23) (symmetric) (1YBO) + a(2)90) (symmetric) yBl2) = e(2)Bt1)enisymeetrie) (eotisymmetic) (eotisymmeti) (antisymmetric) (symmetsic, ‘The behaviour of the electron in an atom as suggested by the experimental evidences requires that the total wavefunction fora system of electrons must be ‘antisymonetri to the simultaneous exchange of coordinates and spins between any pair of elections, Thus, out ofthe above eight functions, only four antisymmetric functions oy. sit the realistic behaviour of electrons. These are: L 1 Fe. 2)+ VWI Fe LaC)A2) ~ at2yhu ans a1 L 1 F (AM; ~ weed] Fy ae + aso) (.12.19) “The above criterion of antisymmetric nature was first enunciated by Wolfgang Pauli and thu is known as the Pauli exclusion principle. It ay 6€ mentioned bere the above antisymmetric principle ig followed by all thse particles which haveaxno 070 249 pu 280d para at Jo wonouquce jweuuLa.p James =u ys "Ua 39 UE acy 104 208 “A worouny one alj Jo wuersw02 Uopezyjewsou ayy stusoxlon jgh/1 20198) aut 218A oO sums 5 200 fo (oN E91 32 (Qr@x CFO (CVO zm(exe dst (OCH Cems COg@st (DACs eo a ute 29] ]duNEHD 304 “BHO suonaoja au) pur (vonouny 2xeo uids poe feds jo yonpoad st yoiy Jo yora) sTeys30 wds wosayrp wese1dad rluuarap aff ul “suoHZ2yo ony ueip 2s01n Bu uy ax e Hua 30 ao YUCUNESEP aU, 29Y 2 go pe tps ponnesayy o|qes ssw au) 0} at: SoAHB SL. "Bxa4 244 pur saNTO amp Jo ofod winos ‘y20u ot 91 ayo yoeo 01 zee sofod ‘ytun aagy suonoope Jo Sunmutds agp yo sste0eq pareausd seuseu Au ons 34 “Suid oysoddo ap Jo ssne30q mq “wonstsan wrsindas onseo-Yonse MUAXEU er aneds oi Jo vorSas owes omy yuoaud ase suorse[2 om a, uodnaya apafsou> aap wos uonenyoo ages a0 90} a1 sn suds ansoddo oxy us yenoio owns o¥p uy suono9[9 ona Jo a0uaseud aU “peuqzo owes ogy ut suos}ogje ow wip alow axey youues a stun pue aout ye ap sum wot! pa Zn Jo 2801) 0} JeanuopY ave woR29P9 sip Jo sAquIME ano} ape Si pe 2/1 —20 Jagan iment uxds 2x8 w 9 “uano9pe BAN 9p p29} 24 3! HON, ‘nea sey uouco 11 2 ‘2/1 + 40) = ‘su anyon aware « 24 oF Sey Caquina inanenb nds }) ou yung} 24 2idoutd uorsmaxa se aun 02 Sup [= 1°21 ‘Sanjea ours amp aney saquiny umyuenb aaz 1) ‘3 uF vonoape puooas 249 304 “(e/T~ Aifenbo Jo) z+" pun = M'0'=] "1 =H! fe saquunu anjuen any a rojo ay p30) Puy a U0 £240 FNGIO St ur suonooja ap Bupao} yo 2idurexa we ZumyeL, TENQIO2uo Ut pawpounuosee 2q ro detp suonoeja yo zequiu o4p wo wopasr 4 seajoNU afd uoESNoXD Ye “suds uanayep 20 ous ox buy anny fou suonoope oat ay sma pu uo.apYp st woe ju equine wnguEND 2 Jo ovo 3889) 38 Jo anyen aut ‘ware axe STeNqHO.jeNeds ox aip UoyA tumor anof 2499 2404 Low Woy wad! ty suoaze}9 Om OM swore se Fes eu wolsxo red Jo many se azou suouo9[9 mt 2th 30} axe qu umdenb ino) 2p 30 yeas Wasa ae suousjs ona Jo ude a ays way 240 vo tye at sz on au pur ‘sz 03 yenba ae (OF ZK 1) 00 (1-21) sue todo + contnet © tapsuosr -cosucnsi) togcngl tontorr -oxncneny L tortoa} oxox -@xcoen L » Kotor - ana) Z rapsueer +casuosy 298 am (eU-ZT') 0 (6211) sha WL pur SS ww pue ju sequin 5 Aes eorsapy av seg swore pue suoyoud‘suon23 ‘swore pue suoroud epnyain si Sioned yong "(so yoy euputies Jaye) suo Togueyorowt wo uous a1 suonsany ap ‘ppoan jasunuksaue ehoge ax) MOO} Soy} pur Us 7:25NH-jey B ON pie suoyud‘suonsej Jo sequin po. ue apy S3jrosfou pue suo! ‘wo om fou a] “svounaY pus suojoad ‘suoxoo[ se yons (jf $27) us estaNyaN reu0 ue uy su0q2013, 0 s0qUNN uoysnyoxa, eg 40 uusog 124 O10W aroun oot f yoogeay ¥ Ze134 A Textbook of Physical Ches 143 ATOMIC TERM SYMBOLS Values of L, $ and J Quantum Numbers 1, Sand J ry The caer conigunton ofa sesgnatd by te tomer oxi anutr mort at unum suber Lae allows Waheofzs 0 1 23k smol | 8 Po oD oF @ 4 ‘These symbols correspond to the letter s, p, d, f, g, ... used to represent t ovbital angular quantum number = 0, 1,2, 3, 4, eopectvel The symbol is als le specie and ight subcited which, respectively represent pin muliplicty («25+ I whee Sisthe ttl spin angular mone Guastim numb) ad th ol agar omentum gant umber (amet ofthe electronic configuration A few examples are Sy, '8, ‘Dp ?Pp?P,°P, and ter element (atomic number less than 46) ig |. This provides information regarding the tot umber (symbol: £). The symbols used fo the me For lighter elements, the total angular momentum is determined by using the scheme of Russell-Saunders coupling, also known as spin-orbit coupling This scheme is based on the fact that both the total orbital angular momentum and the total shin ‘angular momentum are separately conserved, and thus both these q may be determined separately by the vector additions of individual orbital and spin angular momenta by using the expressions Frat = ibe and Sous * DiS Tse glist te coupe o give the foul angulae monent (symbol: J) : = “ J Laut + Set Tessa! gms a tracer by he gunn mabe ted 5 respect The ae of ae mmbers re cometh see oa the knowl o he ui brs ad he, esperch re the swonpoteats of olan momen ed ela ee rene S he ompnr srr momenta agar mone Sr alton compet nal tl momentum, i. Leva ™ Zi bas = (Ey m) (hide) = M, (2m) = 3,5," (Bm,) en) = a4 2) “Term Symbol for (ns)? Configuration Have Mechanics, Energy Quantization and Atomic Structure 135 ‘The s-component of total angular momentum is given by = Laat * Saat = (Ms + My) (HR) = My (HDR) ‘© Fora given value of , the associated allowed values of Mare 2+ 1, which have the values of| L,L> yom = Dek «© Fora given value of , the associated allowed values of M, are 2S + 1 have the values of | S,8= lpg > Ds-S + For given value of J the associated allowed values of M, are 2 + 1, which have the values of IJ a bye U- Dd ‘© The quantum number J asa maximum value when both L and S point in the sane direction, Thus, the maximum value of Jis L+S. The quantum number Jes a minimum value when L and S point in the opposite imum value of J is LS. © The total sof Sare given by + Atomic states arising from the same electronic contig value ofl and S are said to belong to the same term. ‘© states belonging to different terms have different energies, since the intereletronie repulsion is diferent for each term. ton and having the same ‘Thetwo electrons are sd to be equivalent eleczons as they have the sme values of mand We wrt the contiguation 5) ass, where ns represents spin orbital occupied by electron having c-spn and 7 represents spin orbital occupied by tlecon having Psp. Dagrammatcaly, this configuration may be represented @ O ° 0 2 “2 or this configuration, we have m= 04070 ‘The value of M, equal to zero implies that $= 0 ‘The spin muhiplciy, 29+ 1=2x0+1=1 The value of J= L+5=0 ‘The symbol corresponding to Z = 0 is S. Hence, the term symbol for the guration ns is ‘Sya o moo jaoa a o [seed alfonso eI) mio (POO OOO ~/omgo ooO0 ooo (OOM AGO ‘| ar / GOO OO dam 2 opens 5 all Jomo on0 Sa in 6 pos a9 oof ono ago a e a ‘spoquixg wey opooo0g noubyssy oomooG noogog onooaa jeoro o=0+0 Zan pani waysig 6 u8u Jo suoneinByuog anos ‘gqe ut poss ame “py ue Jy Jo senyen sor as Bue suo it IW uoneinbyuog usu owe (7 = A) suosoo|a om Smut Jo KO Jo. (c= N) suonoape omy Suze Jo st Jo Jog sec rwory pu wonoarnong Bes eee om asioye ro2stid fo 70091 YE138 A Textbook of Physical Cher a Ware Mechanics, Energy Quantization and Atomic Structure 139 ‘The assignment of tem symbols is described in the following ‘© The largest value of M;is 2. This implies that L = 2. ‘The associated value of M,is 0. This implies that $ =.0, For L = 2, Mcan have values + 2, +1, 0, ~1 and ~2. ‘There ae thus five configurations belonging to L = 2 and $ = 0 state Eliminating the above S configurations, we are left with 4confizuations 0,0 and oa ‘The only remaining configurations has M, = 0. This implies that J = 0. Configuraion1 = Mj=2 and M,=0 ence, this configuration belongs to the term symbol Cintgucion3 jz and M0 / Comment on the Values of J As mentioned earl Seat ees of Jae L+ 5, L+S~1, .... L~ 51 This gives J = 2, 1 and 0 for L = 1 and Configuration 12 Mj=-1 and M,=0 Configuraion 15. Mj=~2 and M,=0 For these configurations, we have S21 state, 1c accounted for 14 configuatiors ou of 15 configurations listed ‘we have ‘The value of spin multiplicity, 25+ 1=2x0+1=1 The value of J=L+$=240=2 ‘The symbol for L = Hence, the tem symbol for the above five configurations is 'D, * nthe remaining 10 configurations in Table 1,132, the maximum vale of M,= (My = 0. This implies that L = 0 1M, = 0. This implies tat $ = 0 The value of spin muliplicy, 25+ 1=2x041=1 ‘The vale of J(e L + 5) is 0. symbol for L = Os S. ation 10 belongs to the symbol Ine of M, = +1 S= 1. The associated values of M, are +1, 0 and ~i 14 HUND'S RULE the values of M(= M, + M,) a Mya+l and My=+2 M20 and My=+1 M,=-1 and M,=0. Movie M,= +1 M=0 and My=0 Configuraton 9° M,=0, M,=—1 and My=-I Configurator 1 My=—1, M,= +1 and M,=0 Configuration 13. M,= <0 and My=-I Mj=-1, My=-L and M,= various term symbols for 8 Hiund’s rules help in deciding te relative ene Configuration 2 given electronic configuration. The rules are asf Configuration 6 the largest value of $ is Js the most stable amples, For the configaraton nsms the term symbols ae'S, and 'Sy, According to Hund’s The valve of spin mulipiciy, 284+ 1=2 x1 41=3 rule, the mote stable sat isthe ‘The symbol for £.= 1 is P Hence the term symbol forthe above configu of Jin, we proceed as follows ‘The maximum value of Mis 2. This implies that J = 2, Associated with e values of M, are +2, +1, 0, -1 and ~2. Hence, 5 configurations out of the above lised 9 configurations belong to the tenn symbol For the configuration pF 31 °F, To inser the value and Dy According to Hund’ rue, the most sta -Comment Hund’ eis often stated as Hua’ rue of maximum spin mulkipiiy This followspune pa ‘ F owem1ju09 2u0N29(9 a aT wed OA 14 Suimortoa ftom Jo sopuo Sussea01 uu 20) qdtound da Supping rou poss unULAD v st EQN ‘sore snouea Jo suoems ‘ap 5} ajdtoud neqgoe “sry SNOLV 40 SNOLVHNDLNOD SINOULOFTA JHA ONY STdIONId NVBANV BHL SHb stad ae suomef> 9p Ruygdna0o £q su0n29P m8 2) sonpaxda 0 ops se ‘Boudoydwm Aq swore won? fipunyy pue eydauud vorsnyoxo mime (a fap uy mig snoureh om} pay are swonooy@ amp ‘adtouyd aan Aston wow fo Yount V_ OF et aummusg omacny pun woH142A Textbook of Physical Chemistry REVISIONARY PROBLEMS Electronic Last Configurations of Cr and Cu ree ovuseme ‘Cu, etc., may be made. The observed electronic configurations of Cr and Cy Body 11 (@ Whatisa iy? What types of raiations are emitted by such a body : emi cournions fC acy ag d Olreeepe eee ues i See a oe we can write dovin the wave function reduceable to the Rayleigh roprite range of wavelength inci the wavelength at which E, has @ maximum (@) Stating rae = Constant, where A ig of energy due to exchange of electron BE =NxK (Stating from the Planck number of possible exchanges of coordinates between sets of E= oT! where is the tual radiation energy from 2=0 10 =, lel spins and K isthe average exchange energy per set of 3. For as ‘electrons of parallel «bass of Bohs theory, the ater was success in explsining the experimental spect of hydrogen atom, (6) Explain which patcular sep in Boe’ theory was responsible for iaoducing zation of eneray ofthe elosvon and its distance fromthe mics. the mesits and dents of Boks theory. ‘of electronic configurations due to the larger exchange ‘The wave-paricle “The uncertain pi An experimental evidence forthe wave ntue of | energy and lesser ic repulsion energy. Explain, why dhe ation of an electron cannot be desea by he tjectories is inthe eae of Bots theory,wgnpuoe Arpunog ap Suto} woueog Jo suonnfs aygenbo ap uHEGO @) (os) 3 ayeue ajo von nouny mp 229, o +B Bes-v powcoss ap se ue ‘ap owt reouoyds ap om Domo pea ¥ Jo WESh ap 30} oT eveos0 poouey #90 18 SFU }H01 A. gud ars od hI among anwory pup uopecauoni -squonsa> ‘suoRIUNY WoRNgE ngoxd ‘SuoNUN} 2ABM JO SWIEIBEIP OABUIOYOS 2AIE 1u sroquina wenoenb oan exp Jo souwouusts eonsKyd om ssnostC (14) zt oo tl Olt Cee gee eo vonoors fue 1p Jo sot Bao 2 Jo oe 2 wa os ‘an uigo “uonoury axea-y pazieunoy 9} Jo uoESon a BuMojduo Kg (0) ‘ores ap anton) a-9s1 i OYs 2ouaH 2 70 0m 01 anesr Jo Sana ap wo pasoduy aw suonpensal wien TYR spun popstyg fo yoodeeal V- gPt130A Textbook of Pissical Chemistry ‘TRY YOURSELF PROBLEMS [LL G@) Show that the function y-=8 exp(S3) ‘What is the eigenvalue? function of the opertor operator for pi. (© de a contusion gentoo he or a 2 ag eg tee fh as? Uti igre hud not con en inoing gt ge te ea imelvngy 0 2) 12 tne poe Bae ae Insc lar coos i gen by ve Laf.a Loa a 1 a veda) Lea (med)ets 2 Far” ae)” Find 3630) * Finks Big? Sow tht he inion in@ sing, and (iv) sin? sin 2? ae the eigen. tions of Laplacian operoe and find out het respective eigenvalues. 1.3 Show that 3.cos26~ I isan eigenfunction ofthe operator th eigealts 14 Stow hs he eon (y= exp ax’) at Sehtingereqaion an b= Sm i Also show thatthe enesgy of the oscillator is equal to (4m fg forthe fun ction yan (3449) JFeT fr toncon ys (Hint: Bvaluate Hy and ten pa the werms other thar constant equi oer. ‘The constant term is equal to E) the expectation value of momentom of a particle described by the Wok 0 (¥* Lgl WIC W).) ‘component of angular omentum i classical mechanics is given Lew, Wave Mechanics, Energy Quantiation and Atomic Structure 151 ‘Write down its operator spherical polar coordiants. k=rsin cos 9 yersin Osin 9 zeroos & (Hint: Use the expression CCaneslan coordiantes and then convert an 2-3 + (2) and similae ax ‘expressions for fy and 2/22) o*\ac)a6 Since (Lg depends only te angle its eigenfunctions mil be a funeion of agle gon Lat itbe yy P= LP where ft eigeale BY separating he vacables, show that = exp(ril, oli) (© Siee te funsion @ as oe asingle-vaed, i should say he elation DP = P(e + 2x) onton tad othe expresion: Lx milan, where m=0,8122, 7 Te patie inbox fllows he relation lie relaion p= h/2.in the above expression, show tha the kinetic energy ofthe patcleis piven by _ me TE an Using the variation funtion x(U-),eaeulae x") fora pate in an one- dimensional box and compe it with the ave ground stat") 1.9 Show that =0 fora particle in one-dimensional box yields an infinitely large wavelength or uncertainty in poston (ints n= 0 means E= 0. Thus AE=0 o¢ Ap = 0. Hence, Ax is infinite according to uncertainty principle and is infinite according 0 de Broglie (159) gives a= (uh) fk and (dint: Ate carrying out difeentiaton, separately equal 10 zero and E, respectively.) (vam) JET terms involving and constans(:2,)-2(@)-s4 Veryelt x see ea uae 2 a a amy a 09 8 and fn neu stn page oe a SO SERRE Siboseatnnenee sor (ay (Ly fy sean 4 sn, “]~anBop yo wonoany soavaouod © st sean oMeSOMAT ‘jos oa ip sated psi Jo da apeur wea Jo sao [ewsiod =A, w= tay aaxlap 30 sreupioen ay 0 woneUNy snosuatowog3 1 kBiou9 opted aj eai0mp fem ao FumIO=DY (2) YT ase) poe ‘oy = Mx (© oan an 30 foess0a3op m9 SEU ECT sous an eH 70 sv sr0- wo eo~ «0 sto- ee 1 stem cent tan econ 9 en 8 2 0 angen a St aumnaag onuory Po woyemuond) KBsoug “ORUONDERY 280A pace wo 28064 wa uno fo apes 9 2p (@) por ‘onorqoou waved ‘ap Jo tmuawou ene Ye. 2 va 5 uydsGr om u Vonsoqo "de Bupa yo Aamgegand am eH ONS 6 ‘aonoury anes v ose 51 A+ Alo vonemqaion seu Ae ‘OP aoge Jo aq OTE HE veto aut wooed yo 200 pp ae eure we 0 da! in STDIN POROTE APS (©) SL "p< feu J scuses ersousjod anon) porrsosse mn ep Mos os 20 PU Ky ons fwousfod unde, 29 at Jo od Hany 9 HN USC) on oe ‘sousueayemnoutjod anon paresosse a “|= poe |= Wye moyS ‘p= a anan!g erm ‘pus mp1 Soanpat fd TewouKtod aypss8a7 pamoosse aN HH) MOUS, aaa S28 ase yoanoo amy 01 Yoobo ou 5 Asa09 sy Ay UB NETS Smouny io iene aio} p pu (x9 -)hxo 29 woRAUN HOMERS AN HLA, TT Kasrucrgy poorskya fo yoouray ¥ ZI154 A Textbook of Physical Chemistry L vee and the volume element is d= 4nd, (©) IF) = (7) +(V), what is the value of (£) in atomic unit? 1.25 Calculate the expectation vale of r Given: FP exp(- 20a) dr = 1.26 Wihich ofthe following tasicons ar allowed inthe norma elecronic spectum ‘of hydrogen atom? G@) 25> 15,0) 29 I, (@) 34 > 3 1.27 The characteristic emission from pot 770 am. On els [Ans.(7)= Gag 128 the hydrogen wavefunction for = Ihave maxima along the ions ofthe Cartes How many radial and angular sades are presen in the 34 octal? nd the value ofr for whieh che radial distabution function forthe 2s stat of en alom has & maximum or a minim, the following wave fant the principle of indistnguisha 2p and (9p, angular nodes in each case ion and Atomic Sirucure 18S Wave Mechanics, Energy Quant 135 “The electron in a hydrogen atom anda harmonic oscillator have nonvanishing zero-point energy whereas the zero-point energy of rot 136 1.37 Show that Wigan An Viqyy are orthogonal to each other 1.38 Show thatthe most probable distance of an electon inthe 2p orbital of hydrogen atom is 4a results with the general expession 1.40 value the commutators of e ig) and a, (Ans. 1.0.0) (Ws for 0. C1 J ppm e pon spen svar Na yenusod feud voutD-00 ew Pe 5 Soon emg 2.0 OF MOge 5 sN}N US HIG OUP AL, ST as po 2928 on pannbas wore! osoqunuasex pooadno am aero po oq nsumsr# aon «3, tojsouha Anca iudoadd a anbad ‘panadee ‘uy pue WH L0 Jeo ppeai pnt Jo furs w=q a parpsuos oq eu LEGIT tow seu sy) gates poor yy tg ct po ap oH} vondayo Ue ‘sacs pasar 29 poo Beane ey suOHDD| xe Huy Poo uu se) yg apis Jo vog fuotsuourp-ow vse poprefa aq feu 2UG2I0G, "1 Cee 1 a py = adoqs zt sms “4 201d ME) sumsvon 8 320m (9) paw “ovanbay pou am () AIOE a a V9rs 6ecr Choy oss Sze wy, ‘ourmgo asa or 0 paanga Svs apens pose woyy Wound ‘umaoaonoyd ay yong we senuerod Spans tp 20j sea FuLKONOH LL ZT Cot°E 1 ba ‘asioy = adap 77 sassy 0.) "umsioo $ SUN J anh ap ATEAYEEH corpo gue Se orem atz wy fue ee emt et LT cet ME sameseduin1utayp sour # Jo End yous © woy unurxee vos Jo suse ap a MOTH waALD. TL SW3TEOUd TvORNSWNN qwewowy 2noubey, ‘A209uL 80g veya sungeje0.0ud oneipey fpog 2018 ase porsiyg fo yooara, ¥ Sst158 4 Texbook of Physical Chemistry 12) ma? shen (we) ~90.% and subsite in Ea: (ALA) E IL Solutions of Schrédinger Equation for a Harmonic Oscillator Invoking Eq. (AL!) in Bq, (ALA), we get T= me = mg ‘The terms mc? and mg in Eq, (ALS) represent the total energy and rest energy of the particle, respectively. Hence, we write E=Te mg? aly ‘THE POWER SERIES METHOD ican be show that mn in Bg, (AL), we get ‘With these, Ba. (AILI) becomes a 2) Gr ta- de) y=0 This equation is simplified by wing the substintion ye Vax (anes) which gives @y . ey @ ”} af¥ia-ayeo, ie Ys (4p \yeo Gia why ort (gee ans FFor asymptotic solution of Eg, (AILS), we set y? >> Alc such that Eg. (AILS) is reduced v0 dy a 2Y yao oY ‘The solution ofthis equation is veer? Equation (AL9) isthe required expression connecting particle nate the wave nature (.e. A) ofa photon. According to de Broglie, Eq, (AL applicable to ll material particles. may be (a) ‘where Hs a function of y and is yt to be determinedore ty o(ifene- suet omeell zs sien gates io ecncinata (2) eto eons Jo worssaxdg woud fie Kee + TOME [ Px 4K (EX DEX 1am “(@TIY) ba (LT) oF 6IY) soa BoMNSGHS ca + fPolyx 4 ke x 2+ zx n= 22 poe LOX OEE XD HAE D= EE sue + Cons flog + Mtoe + Wy = zs 40 soquiny 24 - 7 40 Snjea as0019 3m ‘sm plost 0} SOURS s0MOd 28 om ‘apoe sp tog pow oye 6 Jo amp 29 EH bg hq anil se souss nod au, 40 UORDUSA cm $04 0+ £04610 400-1 ee ‘indoo uso 3 Sp yndueo 9 204 at209 aN JO eee “(uy souse somod v se pasandxa St 7 vonouny amp “poIRaW! SaURS 319 HL ‘von s,eymauaH se Uaouy st (SY) vonenbay vo ean amy £q panusondes 2q Abus oan(-2) emexo son sya, ore 02 fob feds 29 cyan ap yo peo Jo Sees e365 ana 34 on UOHSaHdaa aAOqR 2203, uontenba soNWIoH st 191 aemonag onuory pun wor i) B10 “SMSO BOHR apquryy porstyd fo yo0qna1 ¥ O91162. A Teutbook of Physical Chemistry f a he and so on swing 2-1 20 mB, ILD ine shove een ep | Qn) q=- ae ge a= = Lew Qu- 4)ag= 2UO= a= FQ0) Qv~ Bay = 2. a= 20-4) 0-8) q2- SHPO 9),, and 0 on With these, the explicit expression of H, for Deven is given by a aglt—28y2s RMVB ye Poy—2 y= a |1~ Fy y 2 wp, Fmv-2 pete Pye a — (alli) Case 2 When vas odd values Normalization For v=1 Wave Mechanics, Energy Quantization and Atomic Structure 163 waves oengig(bot-233 cht RG] wie tajbteealZ as win 4 Substituting 4 ~ 1 = 20 (fom Eq, AILI3) inthe above expressions, we get @ = B09 yy. [amo J eis customary to choose a, such tat the coefficient of the highest power of y. that is is 2°. With this, the above expression of #7, may be ween [ v9 5 ‘The normalization constant ofthe function y (Ba. All evaluating the integral “The velue of integral is equal to 2°v!y/r. Hence w ve osm )=1(rmzyandl g (uw) Galt corssandxo at Aq uantd st g soresado ou oxy) (cu) crvouey sours #18 0 (wrefos0 Jo Sagonb=y rose « yferen) = 4 args) ay 55 wrssnde> ogy Bunmansgng Y 2), ® atuft-2)+ Se oon(-2)- 0 st worenbo 5 mH OL GOL emonag nuory uo uopwemuond KBs2ug SoRNDOR 9805 uv) Fs hyn (Ke Dee OHHH He) Hee rey? a, ® @ Wey Satna = a a D ap env) vy ty ee nf © (#9) BM) + (63) 2 ( a0e) (ty = cry iP (09) SF (2) dO =a RH (ocny >a) 8) 2 ager ‘stemwouhiog (2) Zensen sou S "0 ot pue jouojssaude3. vo Feds tse ony) siewoufiog yuo} Buruyog 0 heya onnewenry Bun paos8 Awoqanion a9 oko woud NH osu a, oveytoso ap yo Kouonbaxy jeosse a st % azaye Gi trosa (24a) my-(40) Ae. Vv) evosa :(Eva)ow-(t )ehe as 228 3m “votssandxe sp Bupueseoy vio sonar 1 mee mas 228 am (EY) pu (CinY) soa wos,» pue y Jo suossaso ap BuamRegnS TTOFa o=az-1-2 2-1-2 ney am (ELEY) ema eri ( a 2) yw asdyg posing fo woomnen ¥_¥9t166. A Textbook of Physical Chemistry Definition of the Ladder Operator Commutator of P and x Commutator of Aand X Commutator of find A ‘The diferential de is related to €X by the expression catty! eget p-—t-(+ fe. 4). P= Taw ai Viv ak) Fax ‘The ladder operator for harmonic oscilao is died as AP +ix and We hve allay) Levers atts, [Ax]= ex - x8 14 yy gfl4) Uy 4 ae Lo yh OQ ya) aft rata) Hae) 08) i (alts? We have [A,X] = Alx - xf, = (P2ixdx-x(P 2x) = Bx ix? — xP yin? = Px — xP niet (A132) Wie have l= 4,A- in, =(2in(@s2)-(2. Phos ween 2)-(F eZ ]esw = LP + Pe 2a 20) 2x Pew] = ple - 20) £0 - Px] (a3) srk Sol) fe ban) 2x mainte amiss)" Lower Limit of the Eigenvalue “ea tinexLsrexd (ak One rhe sexsar pie mal eral atl feetuyer ts anes, Bek ON 8 PEt sama Fax Wave Mechanics, Energy Quantization and Atomic Structure \6T (ass Subsuting Bg (AIL34) and (ANL3S) in Bq (AILS), we get [aa] = Law 228) = ah x 2h 20 = Ff, (att36) “The Schrdinger equation of the harmonic osiltor is iv = ey Dividing by hy, we et Ry -Ey ie fiyeey (alts) vee opevang Fa (AIT) y Hay We Be filfiy) = Av) whch on using By (ATL) besomes (Hf fy = Bld) ie Aly) =e + 0(Aa¥) ha the fpction gy i so an eigeafunton of with an egeaalve one higher or lower than the eigenvalue of (au.38) CContaing operation by Fi, would give Hi(Ay) = A(EW) £20,123. (am139) ie ity) = e+ (Ay): es are postive, n0 eigenvalue off ace bot he Kinetic and the potential energies ae post i Sic ah eK a ee wil be ves ener Lt Te Epand the conesponing wave fanetion for this enery Be Yo008 pur 1+ xar~ XOT =H sat ae 8 oH xe 'H asm soon seam seuousyod aon, 2 830 sonyen agp stenmoufjod arauoy se ws sy aonouny au AY = 2 2G [os ps aucune «jo svonpuny axe ap DHS8 UL a2 KN = @ruv) ayn] (xt +g) = (AY) = AG foe ane aia '2 = 20 corny) (uae 2¥ ORO = ae warner ei) ei) ‘any am 1 = 920) (sry) as "A vorssoudvo amp Bursn kq 9% wou} pourwarep 2q Kew suonDuny asem JOUR HL, (rw) a 691 eamanuys anuory pun uopmmuond) CBzoug “omMOYDORY A, sont ‘om ‘wonury axe Jo uopezemo amp Woy pouAp aq Keer Y IHES409 2, day =A osu sou wove a me °a mek on cay-= ow ‘ax ~ Ap + lam ery) way g eos an esas o= "Aa =4) oss ou fq paueqo 9 ets uonouny seta oi-punos au, ectona sa(Eva)= ty 11V ba) 20030 sds Kg sone 3 Jo soe Somes om, Y ym) aye =o 99 mg ueTocany ep 01 Smpuodsanos anyeawofie a, soni sm. 0= Al ~"2) 30 “Auto =H» 0-4 (xt 0= AK + git + XgI~ 0= AQT aya a) 108 9m} pe 77 J0 suotssandy9 ayi Sunmpsang on aH val on (or LV) ba vo “yy Bamado ony 2°A wn 000 1A v0 “y 30 vamp 3a ‘uonouny anem ‘aieis-punop, souorssaidxy ‘90}610u3 youoyssaidxg uastucyg worst fo yoogen ¥ 991ANNEXURE II Operators for the Compouents of Angular Momentum Definition of Angular Momentum Expressions of ‘Components of Angular Momentum Wave Mechanies, Energy Quantization and Atomic Structure 171 Replacing py and pin gs (AT.2-( resented by the sy a) (A3)-Ab2 2) (bs) ~ ami ay by the corresponding operators physical quantily with overbead Momentum ‘The expression of angular momentum of single particle revolving around a fixed Point is given by Larxp 1) ‘wheter isthe radius vector frm the fixed point tothe panicle and p is its lncat In terms of Canesian coordinates, we ean write raxity) and Peni td tak Hence, L = rxp= (xis yj + zk) x = sp OXI + xp, Gx) + xp, + 9G D+ yD, OD) + yp, Gx) +P, XD +20, ej) Keeping in mind that ixiz0 1 xjn0 sad bxeeo Pash ¢ pxket and kxteg ‘The transformations from Cartesian coordinates to spherical polar coordinates can eee a ee Serco We oo Lm zp, kpc) yp. + yp, 4+ op) a _ (ar) , (28) 2 (ap)a cams) Cee a Gs aH = OP.- 20 )4+ (ep, xp4 + (xp, ~ yp) Since L=Li+l,j+ Lk we get aL %) S+(#)2 (alll) Lye ep, am a laa 20 * Lav }3e HEP a _ (a) , (20) 2 (ae) > ae a zea Bs hesn-yn cata alk Note: The above expression by using the decerminant ne components of angular momentum can be detived Using the fact that 7? = 2 + 9? +2, we get Be rein COV? ag » 28, sin 00089 o oor r iy ae TNBINP a g Sy ae 2 _ rome 12, 18 Log " aor r(sresgas) +2 @ a9 ms) = 48)-(O8)-49)-4 soniey “J events | cram (® 6.u9109~ Sans) = e 210304 (OF TY) ~ (@ HY) sba “seaneaop fo ML 2 exe & Oo fe a [Fabia Somos -om09 non] = : Ges (20 a wya((4)-8 Ao as “(I ) #29 = GI} = ae 08-2 gs} moon. - se, mon we iiadegeay = - = = ______ + — o song urs |(gs00 4) | — = %e nce n (=) _® 22 y 30) ae )@ pon ECE) @ Z F 4 a T ae sagan “J youopseosta > ff po ee Ty re ae 7 ae vm) tee pmo+ oe \8 = 68 om 4 = my uorssardxo op mous ‘Apresty, (2, ‘gus {@ daa3 9305 [t22mss . 22 +. Laungus|ig a0. - (Gse-45 pre * OO Je ) ee ~ 22 (ausg ,s00-dursg ,uis-)| 22 = ra 8 | w er) + f+ Mow © Tigm "Cure EHR] ocen et "7 1 wojsort tee: _& itt? Bom crm roe 4 HM ++ Neus x sere) 22 Iwas Um =n tH OME gy -4(2)-2 inns om wees defeuss) 90/4 2 re kt Ot x se + @(5 +2 use w= WEEP 2 Rog” ag crm (G2!) (sas) + fe me om wo aleEe omy oe (g) ae)(e) | (40)(Ke) _ ee feet eee (Fé (Se +2 we)" eo room GE PAE 2) © 2g 00 uossanso op wos ELL 22mg srUory pry worwzmami KBi2u ‘eNO 280 a on174 A Testbook of Physical Chemistry Operator for the ‘Square of Angular Momentum Expression of Le : f. sing 2 {sinoeas9 2 + seGeee 2 _ = (sin sin m or r ao 2 o+sin?gy 2] (cos? @ + sin ol rsind i (attli6) The square of angular momentum i defined a the scalar product ofthe anlar ‘momentum vector sie In terms of components, we have Bait jth Wit bjt Lb Using the fact hat j= 6 Belge ‘The operator for L? is Carpe) = Z=[ iene) He» B[sa8ca9 2] a seotBeose (seg]oa oor 2 atear2] 9 3) Ea a 7 | . a sint 9 Fe + sin goose > (e016) 2 + e016 2 “al os #{ oan ol a a tab metal eat B08 @ 556 rr seen go ofS os0) 2 + oos0 2 | ap 7 Expression of 2: Wave Mechanics, Energy Quantization and Atomic Structure \75 A | sin? 9-2 ~ sin pcos cosects 2 e [ated agen penncia 2 a ing corpo 0505-4 Bo 9 # a ent eas pain 92 ca consi 1 Bees 9a. 9 2, -kVeomsing z +08? 6 cos cL oats 2 am We have 2 tt Le (oo? a)| 7 Bb, =|*(cosp 2 -coxosin ee Py ("956 36) A a [dsloer3,-snomed] ay af 2392 (cose%) + cos.» X|—cot@ sin Pag? Pe a ; oxoiay 2 (ong) oe sino? E (oe ae? a6) ap 36 i * =- A eor cor) % + oo 0-2 iat Pe? a sat a | -ov ti {Zn brome] ; E (Zong soe Za]| + cot'a sin @ (36 ae" e * a2 a Fifeest 0 2 + cossin cases? 2 Bl oe + orpsingoneca cos pain got 02 aca Osi? 9 2 anne 7) a0 # ~cot Bsin ye0s 9 <2 + ct Bsin g cos Oi 8°28 8 5655 om 3 +8 oun» 2] cxt20 ag! Weave pp (hah a) ea =ii-(42)/42).-42 (a2 Betee(gesltea) “aay omain aian ‘um ura am ‘ova “D sorexado 2p 30 woHsUNuase we 26 A YT ‘smoo) se st Ywawores aaoge a 30 Joord ASUS V seo ip ipo Jo suonunyuedie Atsnoaresnis ‘ua wath ‘nksu109 gj pue swoEI9CO 8 T m9 08 op spp pa sono SL maton 04m) ‘fy =/iag~ gp) * Ffag Ae oH Be (Fo fog 28 2g 2P ase (™) sg f+ ppt P 1 (2) Se we, > = g pom app = 1 upd 24 sao see pn aem9 28 Op GP 2 HD Sf wonouny te 205 Fogelgo 1 por no ype a sma02 HEB 9 “of suonsuny ITE 20} Sog= Sto sof hos “oonouny faanyque we wo aezedo soveade 2809 67 dy 5 ozo SrpmuoovU pe SMI JO SUORFUD HOE A (wat) oF og- ga =(g'a) ‘94 Spnus0> wou 29 01 pres ame svoresedo om omy ‘ou 01 yenbo rou st TEIUNND 2 JL (ary) o= pg-ga=td 2) 2 ‘our of fenbo St soyenunuoo p31 mp0 yoo smumo> or pes aze PEE 2p ssovesdo om AL gp) 50 von Asn ss og = #8 payopaoaadow te 2 sna om Jo oe AL sxoyexod umpuatsoyy xe]nsury Jo sxoyeynUITIOD suoresodo, Bupnwiwog, jo wonounyue6i em SEO , (M8 guy) 2 OP ar zor flee vila 280.9 0 , (00 4. e. jou [of [fom- stone oe) 2 eer nee [te 0 1) + gros LE L e se wy [60 Oe AF | Ey 500 +6 05) 9 ;100+ tt (0 480 ee fo 00 +4 9 00+ aed ve an song pa 7 Buna Becmy) ytqee 7 aarqay, J Jouorssoudxg Aeaspuong poor fo yooareeL VSLi t 178. A Textbook of Physical Chemictry Physi Significance of ‘Commutation Rules: Let the operator commute with the operator G. Since & and B comnsil wo can wie Ghy)= Bey, = Baws advo ie advo = aby Tais means that fly, is also an eigenfunction of the operator Gand i sigenvalie ois the same as that of the function yj, Ths is possible oaly whe By; is. muliple of yr, say by, where &, is a constant, ie, Bye, This equation implies is ao an gettin of with eignahe 6 ‘The comers ofthe above fact may be stated as follows. If there exists a set of functions Yi. Wo, Ybs oon Ws of two operators Gi and fi, then these two operators commute. se eigenfunctions This converse fact may be proved asfollows, [et y;be an eigenfunction ofthe opertors & and with eigenvalues a, and b, respectively. We can write ayi= ay, od Bye by, Now — GBy,= ay r= downs ¥d= ba,v, Bay,= Baw) = Bey) = adva= any, From hexanal ht aby, fdy-0 o (Gh Bary,-0 ats he commu of Gad is xr. f cones ies that the operators & and We know () The eigenvalue of a Hesmitian operator is eal ‘A real eigenvalue implies thatthe physical qua stands for can be measured experiment ty for which the operator (ii) The eigenvalues of two commuting operators can be computed by using the common set of eigenfunctions From these fats, it follows that Ifthe evo operators commute, then the precise values of both the physical Wave Mechanics, Energy Quantization and Atomic Structure 119 then it is not possible to measure If the ‘wo operators do not com the physical quantizis for simultaneously the precise values of ‘operators stand for ‘The operator of pis (h/2ni (did). na (hd ats-(BS) (Pablf = BES FPS = (8h hp). (* -(eta/)-G ie Hence (P81 = 557 Since Pz and % do not commute, the linear where 7 is the unit ops 1 the x-axis and its postion along the x-axis cannot ‘momentum of the partic be determined simultaneously ns ay ha, 2-22) ( ara (3) 263} — Svat ra {a Bk Pate (a ae |*ay,44 97 wun saved 0% ON (H) spo ypeo us oxnusso9 *7 pue 4 ‘pus & °7 simouodwon coay ap Jo oe ws mwOD 7 s0.eado 24, (1) sajna woqremawo> BusoH0y 2H aNey ON ap eM oe aM OY A} (orary) nw) ora (salv) aw) aunsours srwory pu 1 Hs pocoosd am (ry) ba yo pue 7 pue% pie 7 Jo 0}e;nuwIeg } ; smonroy 1 9p osu oy 2 Jo YowD aeNTEAD Of, at) 77D + PI-"1) 7 ey 27°) ~ "7 IAT "7 0147+ "7 pue 284 7 Jo sopeitog wnyuowoyy Pur wnyuowony s8InBuy jo exenbs ou u Wuouodwiog ou, 9g SaIny UoNINUIWOD, sures 249 v8 Aypsooid pour 8 sony ‘voneynuiwiog 949 40 uoneonduy *y pue 77 pue*=7 pub 47 jos0}e nuiWeg Asuna wotd fo yooene vot182A Textbook of Physical Chemistry From these follows that NEXURE V Transformation of Laplacian Operator from Cartesian The vale of (oe = VE) and any one component « ; Coordinates to Spherical Polar Coordinates 1, 06 LoL.) cay be defined simultaneously. By convent (Ge, component of angular momentum along z-axis, which isthe ditection of ‘magnetic field). This means if, is chosen wo be defined along with L?, then the values of Land ZL, cannot be defined simultaneously. This fact isin agreemen, the component is chosen fo be 1, ‘The Laplacian operator is with uncapped the values of ale he components [na ae been defined precisely, lead to the precise location of the axis of rotation Weasyt = (ay which the linear momentum (having zero value) sely known. This ast © ay wl oat the woe pips near momenta Jn Annexure I we have dived the flowing expresons tay Section ction a this ction cannot be Steminetsmaaneoe » 2 gin ooo 9 2 + (aetene) 2,( sno) d ae ar (2) S6*( rind) 3p a. 2 , (cos 6cos g) ge) a Fv Uin oan Zo (s80e e) 2 fl a, (sing) 9 9 78M 5 (4) 6 ‘We now derive the expressions of 37/27, dy? and aac = [inecaee 2 « atone 2 a arr a6 rsind a9 a , cosPeos 8 sing 2] ngeosg 24 Homeaaers | Part, 86” sind 3p] asin peas 9 sinbeos 2, -<2s8e08@ 3 _cosBease a 1p a sing # | 7 D188" Find 39 rsind D799] sosBecose 2, <2 _sindense 2 cosbemse 3, sngeosd 2 sine 7 a” rsint@ Bp rand 9009,ou wet cw (= ‘souo09q (['A¥) “bal ‘S2AQEAHOp 2630 TTA a sudo poo" 05 sx ss we@ wat (ses). Be (iay) e Fe , ana a 08 tg £8 psy PE seusoo99 (E1AV) ‘bal “25em IM, @ asmeunz * oe °F e ek gy EM Be Tae uw” Se 9 508 198 0m “CETAV) PuR (LAV) sba WOM} MON cw E28) H8 (He (2) cw 2) (se) (eh [) 7e te , e “e 23,2 S]-(2\(2)- eet e Wilew se Fe] Cele 2 te, eee em ee @ qn 944 “qn aeUD Sa ear Mak rover ‘se soRUIpI000| uyep am ‘sno}anu 0} aanpja2 Hons9|9 Jo wonow amp 2quU2s=P OY, cro" !| Sanaa i Twmauwasee * (rAV) wet 4 twat, ae he 7 ee = e [om , vege ty T tp." sau * 7 Tamoamause sore 249 uy snayonu 2g oy ane YoRDef2 mooa ap won oso joes jo wp Aan aps 28 (smome fit) 3 + Mosman opens ou ot sous toy fpf Hones epens ML @ (ee San) ao Beouss deoens ede 4s , omg Foe TT wory wadorpAyy Jo uopenbg saSuposups Jo Sumnds TA TANGA 2088 00, 20 s+ 2 ous ous-| e a e a Aasspuayg woopstyd fo y00arAL ¥ ¥8l186 A Textbook of Physical Chemistry Simitarly, we have on the two ses of independent coordinaes. Hence, we can write Fou = Ve Ve (wv ‘where yz describes the motion of centre of mast of hydrogen atom and yz describes the etofion of electron relative to che nucleus within the atom. Sut (avin as bebe tel an (my ae ay ae ze Geer Ye Ye Eis Ye Ye . Dividing throughout by ¥ Ys We Bt * fm \® 2m & Bf im PRB tm ew oafe = (Ss) Some at my +m) Oe im, +m, Oxds nm, rat Similr expressions for 3, and, components are Bd e - am @# © 8x (im. ye - Av) a2 mim dlp Ce ae ; caer (AVL) ( me ) ee am # vt “om 7 ° tm) at a ee j “The frst term ofthe above expression depends only onthe coordinates ym aaa cs tm dB ‘2, and the second and third terms taken together on the coordinates x, y and and the sum of these two terms is a constant. This is possible if each term is separately constant. Writing ‘The Schrédinger equations for hydrogen atorn = Eat Ea (avis) we can write ee -— f— Y= Faas Ye (avLs) e asl } e(e 8 #) ze a | Ss = Bane (AVL [tel ay 5) ade % AVLI6) where + has been replaced b ~My cloctron. where 4 is the reduced mass of 2). the distance r between electron and nuciusis expressed inthe relative cooninates (AVL‘91 'uoouFew syoq 24) Jo 2°14 st Yous WomIoM ajodtp neue Jo yun oymone oun ur passaidxo s} sy, Maw aodkp 2uauanyy 9 cory) a” Wey Caaf) * 2Smpaqonsoia 5 {igio GST ap OF vORDS we joRRIDNS nog ~ ty afzey> 30.3 130 KBouo jenuerod ap 0 spuods mm oTMOW u} possaadya Sf SMU Jenuarod 24H22/9 5 joa 114 otin jeaeied 30 231 iq sYog sy amp ut uaa UP 30 poods oun st wor poods Jo mum arwore anu passaxdxa sy poods ayy. pads ‘p TL r Oxo TseT cee ‘ pets = toy Caaf * Tear (Ay Dg OEXOTITT Sexy, wooxp%y anwore Jo rou sayoy oi 3 2080S Iu, 2un.0y Sty O1XS 150 rare oxy passant Gung ala a, ac) smu, stapes syog. say oun on fonbo st StU, ‘oq ¥ 9 wso1y wi 30 UM aAwOTE am PasseIdxD St BHO] Og, ABH] ‘wapoab is ‘SHU 1S UI siUn a1wOIY J son pos ose am syun xu paauep SuLsoitos 2, sun anwowe om Jo sun uy passaudya aq uno sonnuenb patsy ZOHO LV T=touy pur. T=aqy "T=2 ‘1 pou dss] wore wrt 241203 Bae soweodo ueraongurey 24) “oder? 204 “stysu0> yeotsyd ue yo wapuedapur sotuoaoq siun oftow Jo SULA UI UanBM way soreredo wEIMOINLHEHY oY sug ommoyy TA aaAXaNNV ahi zad ° Ge GBI aamamag 2puory pun uorporsuend) KBiowg ‘sonuOyDayy 2604,ANNEXURE Vill Definition of the Ladder-Operators Expressions of _ fi,ft_ and iif, Commutators of Mand with fi, ‘The Ladder-Operator Method Applied to Angular Momentum, “The ladder-operator method can be used to determine the eigenvalues of squan and z-component of angular momentum arising due to orbital or spin motion of Particle, We use symbol M instead of L to indicate that we may deal with either, type of angular momentum, ‘The ladder-operaos are define by the expressions i= isi, ant = H-iM, cam Naming 7 and fas the laeroperatos will be described shorty. These a aso named 3 the rsing operator and the lowering operator, respectively. We have B=) HM = Wilt, +i, + = (RIP) iit, i, - i, 2) <@-m-(#m) =i? Am, avy Similar, it canbe worked out hat Hare cava) ® = ) §) =(M, =m, ai, it "Oe h hai cava) an be wee ut hat Wit, Ww hi av Wave Mechanics, Energy Quantization and Atomic Structure 191 Ais) iP G41) =, sili, - iP H,-il? it, PP My ouit, 1 =0+i0)=0 avin) ‘can be worked out that Sin i. \=0 ava) Since 57? sad Hf, commute with each ote, they wll have the common st of tigentunctions. we ay wit the eigen expressions as mee (avs) Pree re) Operating Mf, on Bq. (AVUL6), we get H, Gal N= MY Since M, and M? commute with each ottier, we write the above expression as (i= e689) vm) thats, the fonction His loan cgenfancion of 1° with he same eigenvae asta ofthe farction Operating Hon B, (AVIILT) would give BT Gy Tagen) GN = ci. Oo i MyM N= city or WOE =e that is, the function ees 7 with the same eigenvalue c. The successive aplication of ff on F. (AVIHLS) would give i it n=l: » avs) Simul, it canbe worked oot that WG neaii* ry cave) ‘gation (AVIS and (AVIS maybe writen together as it ti =a 9 cavmns) Operating M7, on, (AVILS, we got MY) = Mov) «avimLt0)xe arta) onty XE atze—2 ssf om -(ecUAW) ba Bun vom pu yy Ka" Buea Sea ay 22 corm) ay Emig 9 sat ify 2 (rmw) of fap wee seuoseg (ay) Bg Bs vo uo on) 28. 4H wy Foes crm osen pm OCH ug. £9 30 pornos" sey smug -pousies ou st (QP THAW) bal, 20 1 WN soTeas8 Jo. oMEA 8 sO wm, (*2 yg) =, 7 (haan moe maaan ayy oe ae se vontam 99 eur suonouny Siypuodsou09 ayy, *Soanoodsr ‘suoneurqatoo sm pue syd 03 pa se prwosaudas 29 asa 227 "spumog sod 2404 TY 49-24 2tp ‘poo SPloy GL TAY) ba vAR J9pI0 UI 730 ane a seaIoU YI ‘Soseazour Za puoaes ayp ays Rysue> Suewa! UD say ap (QT MAY) ‘ba UT orm) 2 (2% oz (“184)-2 ‘ney 9% 2oudH“Soneaue anu-vow axed yom 20U2K i ots aneSou-us 0 podsonoa <7Y puE jy EMO oH, ag | (Bre4)-sfaurmegy ra ‘souroaaq (ST TTA) ‘ba Suse vo yor (a? = 2 EW + HD se (gTAY) al onum weoam 2 yy * Spy + =H = Wy ous Grmav) aw tay (Br=4)= \cgwe(ta3) fr sagt vei om (pA) ba v07Wy BuneIAdO, 61 2amonutg aruory pro uowerrvong) KB. ‘sorUDy2ayy 26044 ovmay ea wl Zr+9)-quw may te) Giwe=U3W J ney 2M 20H Jo sesso paoedsaze?yy Jo songeausli op ep sKeyds (HI ILAY) Yonenba, cvmav) cryo(Ers4)-ayow sv sso wenn 0g Ae (@E'TIAV) Ove (CELHIAW) SbonEna 3 a(S 1-9)-a;aw yo palo ues am AES Germav) cermmav) cw (Bree) -cyr a oo 24 Sq oa om any yes fone (NAW) “ha Wo“. tops sapcocas % ary(Zera-uwe® a nly Sp areas o=cn lw HW ‘s) seam (IAW Ba Bug wo eae weno n =A WN 28 om (er Ay) ba wo "yy Bund soydo Boe 2 5 9 A oo M3051 “pen oie oon 2m onc ote tin oh csp sored Bap oop ay 2 apd quo 2 eer +4 onpanis ua yo maempia .¢7 NoteMy on Aw mw UMan+o=un ny» aa'n= ann ‘n) none VTIAY) “ba ‘SR WEAN. (may ‘wy a wc a aw ve om (OC TIAY) ba OHS 2 pueq sqwersuog 21a luoomiog UONE|oM assnuryg port fo yours ¥- zt194 A Textbook of Physical Chemistry Eliminating cin Eqs (AVIIL19) and (AVIIL196), we get hk Bhan +E bea ® Dn bade an on ‘This expression wil be satisfied only when me in mele b-rfe] ee) wn meee (8 A) oo tae (EVE) vm “The expression of c.is . cnt (S)iee(S 3) +) a) SEY wm Waiting (e+ #2 by 1, we get Pag == 12) cave) (AVII25) Since & changes in a step of (Eq, AVITLL4), we cover he emie range fom rg Pa BY wing the expression be mee) avs) neem varies from Io 4 wth a stepwise incense of one. -€ vm ‘The vale of may be integral oc hal-tegrldepening upon the even ora vue of (Case 1 thas integral vues In this case A= K” ands = 0, (Eq, AVTIL20) Worse, t= EEE gee Fortis case, we have Hii =[o( BE) Koa ns m=0,2122, 441 Wave Mechanics, Energy Quantization and Atomic Structure * 195, bya Bein, asa Wek Weed = tee =hattitegral values 2 2 For this case, we have Naiin=[(A)]diin, mesbed ut pcr Piinsasv(*f@in lds Gineasv(s}@in 38 The cin Yen onve ub Fad mani wen at 2 (ay B yeetern( iat (2) tn smn riaeo(t) ta ova ‘The subsript J and min Y, characterise the eigenvalues of 7? and fy respectively As stated above, the value m vais from 140+ sith a stepwise increase of Since the component of angular momentum forthe function if, Ys 2x higher than hat of the function Yq, We may Write the function MY, x's HXn= Kawa (avis) where K, isa suitable multipie. Similarly, we may write MY w= Kina (avy raluton of MuliplierK, Milne side of, (AVIIL3 by its complex conjugate followed by integration, we get [Ost Bion, 8 = 2 [eT dt cavm32y) Assuming the fiction Yt const i= [ity, we get inde = [tara Me +18 Mgt = [Gi Haigds +i [Gay Naas avm33) * We assume thar the molpir Ky hae real value,(oe 0g we 2 aug wo — 28.5 soo) Mi ° (gemom-oe } 7 1 $P ou )our-? | WV - 4 (Pose one + Mou] SE -= @ @ sont SUE 1=ép0,0f “yy sveedo oy, yy fo waste oem oan ‘1 '@ vonouny a 70 oMezTPUEOU a4 A pouTUNE. st Y YHEISUOD aH 'TE'TS'0=m — jrpoo' prow ne SmUL T= (upuz) wis + (we)s09 2 °4 wonuna sexo 9 Sian 4 pomcip 9 ur aom>any ou, exp aoyitojcoudeg wT 10 eda? Fo0ie¥ 22 omy) (2)oeu= nap» vba 49 <4 wos pane a0 (woes (cmav) sup¥=@ 20 wEsuO+du=g uy] — 20 PIP AMO Paypows oq wed w MPUMIS TIpsosoig “y zandympy Jo woyomposy 2) ope? _o Gem) (Z)aewsnm-opey pin= 2 30 gu 2 (ar) em peop : se a ston ocean Soong (Brena ae (Be aaron ‘oto (2) uate wn eee wrveal BH()- Se Bheen]- : oruen | \4S)-Bo- (Zan 49% (2) wag 26 ao (F uote walcegire aff = “win wns nes cn)" = aneyon dele (za) ="p1 2005 2 Comb (Buren sek + ne yh =a orssaxdxe 2p Sun B+ WCW We Sq pourworep 99 Seu vonsuny 9p Jo os 94, 4 HoRDUNA 2Mp JO WE Gem) “oo =" 5. vonpuny sp asa aa ‘sexqetNA d poe g sasqonu, “7 soreEdo an OMS taf om ‘worssaxdeo oxoqe ay Jo Tenfuo9 woydwioo oq Zupye, spencer Gna = serena ce) are (20) 20) Canes yf = ‘(emMAY) (Sox e) (oY = sen se emg =27 (a oe Ed 3 [Fess dsonproors Geom + 40 =. se soni 9 (6 HLA¥) By 0 Stal my Ss 61 aamanag opuciy pro woworands KBioug ‘sonaDyooyY 20D) Aassruoya qoasstyg fo yooqnes ¥ 961198 A Textbook of Physical Chemistry oR faget oe Melo Hence, the function ois ele Pa ‘With this, the function ¥,« becomes Form of the Function ©, Substituting Bas (AVILI7) and (AVIIL1) in Bq (AVI), wwe get 20,2122 00 caving) cava, Expression for the Function ¥,,., (faeries tae) -* wm (eed oeran io co or el 0, +icxae, He¥ 30 a6 aeide ied gy ne ce EE Oy rico 00g Cite" =0 This gives, a 4 6-1 @090= 3p O-1G09=0 asin) ao cos ce = loot 8401 - sin e iad ‘hich on integration gives In @= Fn (sin 6) + constant o=t a Basile xs econ is dt isthe srtn ofthe anon Oy singe apa Jororeoar=1 cavmss) Wave Mechanics, Energy Quantization and Atomic Structure 198 Substiuting the expression of © and carving out the integration’, we get vay vas e (:") cava, arr ote nn Fg We Be i (i) ; coms +) (sing 2 + cot0 cos =(-B)lme ge onoene ss a a “igh (0g, -oreine 2) cos? 648 int oy ono) = 04) ovsal( gh) fan “(eal an@t—2)--2 3 @nar=a)--2usm) osmw) (souw) ote att 428 9 (pS THAY) ba uy worssondeo onoge oq ZupmaNSANS 9,809 (1 - 10g 2umanug uory per wowvcanarngs Raoug “onmysoy 4K, Pg S00 6 H8 9109 1 = Sol [or oe [[svne)for0 .es1e-)]x (Gov) ea -)=" ow mow 74 (Baume -w 8am wpe nf =" soda op Buys 1=m303 otth xz -) Ve $rIAY) Sa Bugg 2)(@)- (ore 002) (n- aL) (Z-)= a \E)ae +4 (Z) ap =(orm0,, sso UyTAY) am T = -preouy )- iu) ok Jo YO4DAL V OO 7 (om arene eee oe a [eWave Mechanics, Energy Quantization and Atomic Structure 203, ANNEXURE IX Electronic Transitions in Hydrogen Atom including Spin-Orbit Coupling ‘The electronic states along with ther term symbols of hydogen ator 1.13) areas follows Section isa 15212 160°" TST ear Configuration Term symbol e 1s, 2s, Sia Pia, Pra Dyas Den "Bo "Pin Accorting to Hund’ rl (ee, Setign 1.1), the lative energies of stats follow the onde: g na? yy <*Syo< Pa n=3 Bin < Syn < Dag = Pra < Dyp nad Pin < Sy < Dy = Pya < Fag = Dap < yy While discussing eleeonic spectrum of hydrogen atom including spin-obit coupling, the sleton rules to be followed are AL=sl ang AJ=0, 41 29, Seren 2258.9 ene Some ofthe allowed electronic wansitions in hydrogen atom ae a follows Byalls) Pyl2D) *Sa(38) *8yn(18) "Pag 2p) *Pra(P) © *Sy0638) *Pyp(2p) —"Dy230) P5n(28) <"Pya(p) yp) — Dal) These transitions are shown in Fig. AIK. In the ance of spin-orbit coupling five spectra series (Lyman, Balmer, Pascheo,Bricket nd Pond) are observed. the presence of spin-orbit coupling each absorption is found tbe more than on absotption (observable under high resolution). ‘The states Sp and Py are two-fold degenerate corresponding to m= +1/2 and -l/2, The states Pyy and Dy, are four-fold degenerate corresponding t0 m= +3) 2, 4/2, -1/2 and ~3/2 The state Deg is six-fold degenerate corresponding tom, 2,372 and ~S/2. These degeneracy az lifted upin the pesenceod f se on soe axle ogee eA “xv) “ba Sonmnsgns jal! = GA ‘se suonouny wopouny a4, a) aan Buuepisuor to 0s pur (onwabo uopegemed ps0) (wogenbo vorociaisd pian) 18 am ‘wolesadxa anoge ap Jo SOP OMH UO 8y 30 suofoyyooo atp Suen Jo ones Aue 205 poo TA DSA Dee A gl #64 IDE Cot Ghat + Gat + Jo uommnsang 0 “uonegimod 29px sae exw) ae tt $e aamomaag srwory pum worenaone) <2 ‘soKIIZORY 24044 xe 1 Jo mod st ev pope ag fey St pe YA goa oven Sut" med ana pai ny Sond ot yee Sues poop ons ya Mama onoay axe a -(eoneansad yy open word upnpaA wn os pgmuadn poner Sonatd yo ona us poupoap aq es Yona ed aus fom IAC gl) ss waning feu was puma am 0} vos Bupa ou, oxen vormaiund o pousa Ue (2) ‘io tomes een unos on ap J kn poms wap 30 KEN yp @xv) ox xv 2omaado 2 ut uopreqamaad ay 1 pe “Steanoadses"z pur | suan9,2 20 sopessdo o¢p Jo wns st yom) redo pogo Sty ays 1 wow unio 2495 sye20do weyuonNy ayHORDaLO SHY, Aaoayy, uopegannag .9PIQ-ISI YX SRIAXANNY206. A Textbook of Physical Chemistry VEU Par «Bf VOY bef yo" 9 — £)8g= EB [vO H yar Kronecker delta (6 = 1 for m= j and 8 = 0 for m +), The above ‘expression is equivalent to ag EO) ~ EP) = EB J yt Al yar (AX) Form=n, we get ax correction in energy is obtainable from the unperturbed wave function y/® and the perturbed par ofthe Haziltonian, ‘The coefficient ay with m # m in the perturbed wave function (Bq, AX.) as ‘obtained from Ea, (AX.12) is given by ax provided £9 « £0. This amour to which the ‘comections are being carried out must be nondegenerate. The coeficient 4, may be determined by normalizing the perturbed wave funtion , (= y+ x19) APPLICATION TO A HELIUM ATOM For helium atom in the ground state, both the electrons are allocated to Is orbital, for which, we have os czy" 2pm Teen (iz\\ eee ct = RBeot =A2) 2 4-12) o “ ) Te #() UZ Yate gai axi9 te) The energy of an electron inthe orbits of hydrogen a8 la] = Hence y= Wave Mechanics, Energy Quantization and Atomic Structure 207 Hence E% = £ “f mn energy is given by | 6ev)] =-1088e¥ (xan, (x18) The element of configuration space in the above integral is wk dan (axis) 248389, (AX20suaywonfo A pu 7>x>0 30) YHA uossaxdx amp &q wan ABiou9 penuarod oy paratgas st x09 ap ut ajqued ay) asoddng ‘esoynana = pun) >*> 920104) xo ROROM-H0 8 WRIT ed X08 TNOISNaINIG-3NO V NI TOU V OL NOWWOrTddY ‘9.6L -S1 ne jruouud ay, AogtL ra ee ‘qe eaten) 4] * TxS 2 1) zs~ \EG) 298 om '(12"X¥) 'bg UO (0E"X¥) ba FueaNsAES exw Avore=(aroed = = (2) ay, exw) “(Be PBs Bansr tai am 0/70 = 4 200g 498 = MO_ AB, 91 Co) so eto” 9.) wer exw Hh 10) ier wow iB pepuers ap SuIs0 NON 60e eumionas 2pwory pro uowenmuont) Kus ‘SoRUDYDORY 24014, o {2 @ 2.Jfon ) (9) | 9) PDO) soy, 9 =9972¢ anna om 2 “osty “=e amnsans ome 5 85 fy ue OM Sr atoyusgns am a 5 45 0 au xp uy vagy“ sano say aesRo10 a JL sons acre) (2) Kasspuoyg poor fo yoaray ¥_ BOT210A Textbook of Physical Chemistry ‘he tust-order energy corection is given by Eps Jar. ae vor (E] secant: where a= fm (hi2x) 3 (may be called anharmonic P| © potential energy of a perturbed os oscillator) be given by ved geen eet! z where Wand &" are constants, In tis case, the peur Wake ‘The first-order comection tothe ground-state energy is given by Wave Mechanics, Energy Quantization and Atomic Structure 2 (J [kos fovea] SEO] S-e Hence, the energy of the peftarb eis serine Kiln)3) pue 9 stuacujooo yo sanqes an sprawl (1 = Usg'92 + BS9 + Ug 8 ‘uayia) Ao wolssaxdes vonetmoy ai ie Se stonenbo seno35 wt 200 Kg 00 ‘noge ai anf% Bea 200 8g pu gt ley Ey Ny yo sonyea ap EeMOUyy o= (sa ~") ~ (5a ~ Sasa ~ "y) ane ong = 8p pue By = Py aos 0= ("sa ~ HY@Isa = 24) = (sr = @H "sa ~ ") sane Buqwedo uo yor. Psa" Ysa ~ "Hl ‘warsks om yo ABuous voexa amp 01 KBs9u9 ay sate} ayp‘uonoUn ‘aynm 01x of 0 voHDUNY aM Jos0)9 ay}, "NoNuRY ax youn sree ap suisn Kg % uo punog skin ayy aeyraye uo as ey) 8408 UONDUNY HonezEs 24, °gzq 0 oz%y-a mx) o= ‘sa - OH ‘401020 eb usuuDa.p 40s ap 1s a Bsa o YOO ANION 3x CL, lotta" sy ~ "Hl tllesa = 8 uo) oro. a if = sq Bao ao oxey fu 2m 402 “D49 osye pur jo sanea ne 303 °9 Zz omg 1859 = p19. o= Clsa ~H¥9 +('sa—"n!o saoqenba sejn93s Supmoqey my & speaIQ = OEE worssoxdxe amp nana smotogo09 0 yoda ys ous yo woqeztmnUN (rmxy) (aya) =%5 =4¢ pur ((Ai*H'A) ="H="H aH Bstobe+ Bla + THobe + HD+ 7 Aig +A) (Ala) HAA‘ + 'A'D)) (AHA) st ossan £8009, WO+A=A re1p yons ‘soyoured onus wopuodap Sqeauy om asyosu WoRDURY aA B 2 1 paonpat st wowssaudio aoge 249 “5017 AL 0=("6|%8) pur y= ("S| 8) ‘as juttouoguo ws \ce0°S)) tale) (ap stat (Co9°R)\Ga°S) alow (ors) Palee'g) Rua samy om nn *e0"Z =a yn 77 sopeado weqvoxraneH ay Jo suonaunjua Jo 1s feuoUoKAO ay du09 yo suor wt popondo oq vA opoony axe Loe par om oH ‘smoqoy se S908 ma!oamn uonEMPs at Jo 00nd 42 Weroay], [eUOHLLIA JO JOOrd 1X AANXANNY214 A Textbook of Physical Chemistry Note: Fora wave function involving » linearly dependent variation paramegg (vey = E,ciyi) the secular determinant takes the form of BS; Ha ~ Bp Hay ~ ES Fy ~ BS ~ BS, Hyg ~ ES, eee fig APPLICATION TO A PARTICLE IN A ONE-DIMENSIONAL BOX Lethe wave function of a particle in one-dimensional box (V= 0 for << Jani =e elsewhere) be given as Y= Civ + Cave where yi = A(x) and ys =2" (2), To evaluate the ene following integrals gies, we determine the y= (yall) = (ad wa fe £ eee ieeae \ of A YP 2 (ux) aera 20) (gi rahe -GaI5) = (Was) = (xt = xa») = fee +x 28 lae =F h 0 Proceeding similarly, we in that toate (EYE) ‘ A Sip=Sy= 1 Wave Mechanics, Energy Quantization and Atomic Structure 215 (Yor) Ha= (4 (8 Lint Ais) ? a With hese the secular dteminat (Eq, AXIL2) becomes (era\5)-45) Gale)-Ae) hantmA3)~ "\30) (extn A ts) ~ "Lia0) | 9 la \2) Ae) (e Y)-4 Kan?m Ais) ~ “L140, live \i0s) 630, Let K = 1?8x?ml*). With this, the above determinant becomes 5 PG-§) 8) sl, pf(l_£ of 2 E LE) ap 22 sie) sae where E’ = EIK = 8x’mPEUH. \_8¥2_F) pat £), 2 Slate ae) (is ta) <9 ‘lying throughout by 1260/K7I'*, we get (420 -42E) (24 - 26") ~(84~9E'=0 or 84(10 - E’(12-B") - (84 -9EP 30 or 84 (120 - 228" + E"?) ~ (84 x 84 + BLE?— 84 x 186) =0 or E784 ~ 81) + E'(B4 x 18 ~ 84 x 22) + (Bd x 120 - 84 x 84) or 3B? ~336E +3024 =0 o (E7 = 1128" +1008 =0 a geo tiz MIRT=OS IO _ 2 VISE _ ura a6 ~ ae 2 2 ener a Su=nf ort 'g 2» (ty 1*A) mg 2 (ALIA) ON (ay \ (Arty tA) 1a am ‘pameunou are A pue 14 sours 24 2su) wa) (su) | : cee 4 a 2) (4 az *}* / (11 AY(A 1 ear 1A) + (2A 1 2A) eae (sal \ a) cae [epuglteame) , (oan) (us) Je (sal a, el mh ey sinha) = (ain) =9 vont 5 wore ayo Sava wom (ay) | (Pome) (ou) PF Pa- 2 ee (tose) | Pais) | Ese) 2 Baa)" waz) sus) mat], [xm : “a ] «. (omxy) +g tig ee wd sm, (e8seup seayon yeuen ay ose Zeqonu a Lig simponug query pun uoweey iQ Ag ‘sonmyoow anny, {29899} (Yo%eMs) aah =A sy vooary 2m pom si- poo: 2 vwnyayjo sorsodo ALAWVuVd TNOLVIEVA ¥ SV WOLV WNN3H 40 3OUVHO HVSTONN pols Pe eer sy wonsany ant pateusou am ‘2ousH dip [vert = (OUT De (lf feOPD = (UID TD ='9 +o appor= 9 = ool) Tei (oa (222) uoe+( (oe) (290 =( per(%)o+( (7 Greee- (Be Gade pon 1a tebe 4 Bb + so opsadxo voeayunou an sup BoRMSGAS (OVID g='9 > on (MS) +(E- Fo ise JE is6 1)” song StL, (ees at 1) M08), ah 186) dt | = Cisa—Hinta + ("sa - "9 128 om “(rpEY ‘ba) woUmNba os UE 7 Ba 8S usspaoyg yorskyg fo youre, V9It218A Textbook of Physical Chemistry ; “9 Since Z=2, we have n re a ‘a ‘To minimize E, we set @EIAZ' = 0. Ths gives ') (2-2 eye =O Hence Z’=27/ Substituting Z'= 27/16 in Bq, (AXILB), we get e=(2 \ nyn) =- (22 )iscev (aleh ) 2-746 eV ‘The experimental value 79.00. Wave Mechanies, Eneray Quantization and Atomic Structure 219 ‘SLATER RULES FOR EFFECTIVE NUCLEAR CHARGE Forteliumatom, wehave 2 = 21/16 ‘This may be written as, z= 2-56 where the constant 5/16 = known as screening contribution, The nuclear charge observe by elecuon | in Is instead of 2 de to the sereening of nuclear charge by electron 2 in the sume orbit i. the electron 2 screens 5/16 of charge for electron 1 and vice versa, In general, we can write Z=2-y) where the sum is overall te occupied spin orbitals other than the one considered. ‘The empirical rules, known SI nuclear charge as observed by an ‘The rules to be followed areas follows. 1, Por the spin orbital j from a group after that of the spin orbital i, the value of 20 ie 2. For the spin osbitlj from the same group as that of the spin orbital the value of) =0.35, 4. For the spin orbital from a group appearing before that ofthe sin orbital ithe ne of al isa dorfor 1480p orbital when n)= 1, ~ 1, otherwis Grouping of For valence electron $= Esy =(2x085) int Zen Z~S=8-3452455 Mn: Electronic configuration: ( Grouping ofthe orbital‘ap ao4ig “font jo saevipiono ap Uo spuadop "re ay pau oq Kee wea ‘ha ='ACa +H) A vonouny axe sean xp pue ed hg =H {6 pauyp st A uonSuny axe uOND9f@ am, eo wea aa at ‘sm, ojo Jo SEU et Uo Auo spuadap ne] ai, pom yo 38049 $e Ta Se SuOMDe[@ 249 Jo saTEUIpIOND 2X9 UO spuadap {oud} ay, "wonouny axe se3FoNu ay) pue UoRDARY axe amUONT2 Jo YonpONE ‘ap se vopouny aves jo agp dime Xq paxorype st vortemrxoxdde anoge 24, seoueisp rajoruon WeysUOD tps 2m UL Pox “«2iouaayuon2ojo amy Sunenqeao any ue deme aynaqorr xno Az SUED 2p “2UDH “A rene ooeds ofp 3o sostanEn poseq ss, "uoneunvoxdd sauraquaddo, og 3o dy tn tim paxouras 29 ue (ezz ba) soredo ueywonpueyy ayy wt wonou wajonu a Suuasanda: ws} oN, NOUVWIXOHddY WaWNIZHNAddO-NHOS, cera (ero Vee puog razqoang fo suoays, = uty) Lt weve 7 ia : 323 E™ a q ‘Aq waar’ ame asaqy,-suLia LOnseaTUY snafonu-snajonu pure ‘uoNDs|2 EE somone uanoyrsmpoen om anata! aqunp par a a eo Catan 44 wan st sore weno 7 aa= aH s suonoayew pu pau Sureeuo> qoqouv 20} uoenbo 38upanios oy ‘wopenbe JaFuIpquy>g ayy anos 0 se wan>2[>-KuEW 2 anasto} SU sporrow syusrvoxde ue sonjeauatie pono {4p uonenbo 18 ‘jojous om suas MNO fT Pu A[NaTOU aM UNE Ie Jo souIN ap _3pun suono9fe 24m Jo moweyoq 2M SoqUDSep yoRyM UoTOUN aan W 3 Sto KQ Peaussap 29 Kou groajou wozesaow vaue amy on BuyuoaDy ‘sonmeyoew wan & Paprowd vey axey puog yoqex0> Jo uoneuAo} ay oj HaadseaanenEnb ay, ‘woe empty oxp wtp aqqes aos Keone Sues nou ap SL jar apesonpoyo aq Suseaisep s9piseq wowsBuee sore ow 2 o uo yen an Sa red uo so} pays a, suonEAN UL woneanatu00 bot wow ypeS Sdjay ssTed vonoapa Jo Bovey typ, “sw HOMIOG 39 Jo Fuwys a9 9 np wD} puDg WoTBACDw PooUDSOp CMM SUAS 9 49 poprnoxd sem puog wayes09 & Jo uoReunos2xp ang ammo aatenERb ay, puog yuapeao; Jo sar10ayy, Noluvnda YAONIaQUHOS 4O NOISSaudXa Zz NOWONGOULNI bz *2224 Textbook of Physical Chemistry Theories of Covalent Bond 223 2.4 TWO APPROACHES FOR APPROXIMATE SOLUTION OF SCHRODINGER EQUATION (One ofthe most important ways of constucting molecular orbitals the scheme based ‘on the approximation of linear combination of atomic orbitals, abbreviated 3s .CAO approximation. The choice of LCAO can be rationalized by talking an example of a diatomic molecule AB. Ifthe electron is in the neighbourtood of nucleus A, uetcuoic ery, fo he ven ineracer tances maybe called y Saving he Serbdnge equation a given by Eq (233) fe Eade 241) the above equation cannot be solved exactly even if the internuclear iy, various approaches have beea in of Schrodinger equation. OF these, the following two approaches have been widely used, such that it has characteristics possess Vj i the MO shouldbe reduceable to AOs in the extreme cases. MO asthe linear combination of atomic orbitals. Mathematically, Yuso= Cis + CoV 42) where C, and C, are constants which, respect the functions yq and yp. Inthe extreme situations mentioned above, we will have , = Land C, = 0; when the electron is near tothe nucleus A, and C, =Oand C,= 1; when the electron is near to the icles B. * The molecular otbital (MO) method developed by Hund, Mulliken, Lennard. Jones and Huckel ‘© The valence bond (VB) method developed by Pauli y, ae the weighing coefficients for sand London, Slater and nthe molecular orbital approach, we look at the molecule as @ collection of ‘cle and electrons. We build up molecular orbitals for collection of nuclei and ‘hen assign electrons to them, The valence orbital approach, which was developed riot tothe molecular orbital approach, is very similar to the classical chemical ‘concept of valence bond between two atoms and to the eletron-pair bond po bby Lewis, In this method, the molecule is considered For any other situation C, and C, may have identical or diferent values depending ‘upon the nature of atoms and the associated wave functions Ya and yp. the electron distribution is given by the square of the wave funetion, ths carried out up 10 ‘Trial Wave ‘The basic principles of MO method are very similar to those of the self-consistent ‘The normalization criterion applied to yy gives |S ertepammerae “Toaurc ce Functo : Jrdostate d Jufers of vjees 2605) vaste Aescribed by a wave function, known asthe extend over the entre region of the ‘Assuming atomic orbitals be normalized, we get eG + 266:5921 Where Sg i the ovelap integral between the orbitals yy and yy Inthe zero ‘overlap approximation (yg = 0) he normalization condition is they are polycentric, ‘© The significance of molecular orbital isthe same as that of atomic orbital, Thus, finding an electron inthe Volume W y"dr represeats the charge density in the volume clement dz. Al clement de * Each MO may be represented by drawing contours of constant yor y2 o by Arawing a boundary surface which includes the majority of charge cloud + Each MO is associated with a def ich may be calculated by solving the appropiate S # The allocation ofeleceans 19 done following the aufbau and P G+a-t Inthe 2ec-ovedap approximaion, Cf and CP ian numbers are evaluated by densities. Thus. the gross atomic lecular orbitals of a molecule is exclusion principles,yea oro7 ancy ttm My pur %y oq wan pono you op SF pur YA sTeIaIO BUI (6) Pe (Hz) sha oH SpoDNP smoqO5 (2) W -anoge pars spa09 a soncad sty ous Aro 51 A pur Ya usow Surms e A Sey age a, 5 2 mA ones Beye ay poe » rng A oF pes im wary ep seoioy m oansedsa “ip pu Yn on ssop9 fen axeg pe" 20mn5 “3-40 5 nq“ 205 pue a Seay D em pay am (o'>'2) “ba wo Trig ‘A soy ‘eanvodsa pe Ya oy sso Aa sonen anny ny pu “yp Sno oro 138 am bo = soy seen on eoday om AES a wy ero Tre aR a NS" — 8) = %0 - %oVlg ~ Yo) won ‘sng, 7 ~ 99 wun ayy w So = 7 Bund Aa poxorype oq we> (12) ‘bay UoRRIOS esodde 2p wa es mis ® smug ~ 8 (evo) ‘ba jo wa 59%) =@-"NG~"9) oo 0= (sz ~ 9) - - Ng ~ Y) St puog surroray fo souooyy rpuoo au (2) wor 09 ano 8, (4) UOMIPUED JO, worn 0= GYD + Osa - M9)! wre 0= sa ~ iio +(a -%0)'9 suortenbo sou snoatmynis om Sno quan aa 8 A pur YA eng omc om AIO euganot q pou; senqos22(U oma oso pe yFUI309 2) oH] eu a Uo 29 TS TENG SH em awooese AnD om pe cro 8425 + Yay = 084 F ——_wonouny peur ap Sumeeas Aq poured Aste oq eo ‘tqiss0d se yonur se 23910 oro depono 8A pu YA yo spnoys afiey> ap 3129 st UomENTgUIOD aL “Z souoyp ‘mv 284 SOY posfoaut Jo safiou9 am se annsayo 99 ur Aeu. “40 yy se wom ‘aaofoun ‘eu 9 oo tp spensnyy og, sone aygezeduion aney so} Aannoodsar som ur St pus YA jo soduoua ayy 31 neq sf uopeutatNO> ou, “t stone} Supmoroy an 9 pourmorap am SOY 40 Sye1q1 orwore soy w Jo voneUIgMIOD ap 01 W “Pej uy ‘st senqio apuore jo uoneutquio> 308m] = uy 9q Abu) mop 8 Apuo pu Son Sq, Teo zejnoofour ayy Jon “Popa wre se owt of2q sTeHo arwoT Jo soquiny Aue 2pm Teuqio mmoye 2u0 Kuo apnjout am yey) A2¥ss200u ere asf se vont ‘uonzeuod Jo uonypue9 a 1 poroo(gns ‘poqiou vonmes au paummsap axe > pure 1p Jo soayea a4, arapyp om 0 | wow yove + pe Ms'5'9+ ban 0 @ pO y suow bo ied Aaspucyg porshyd fo yoonsean ¥ vee226 _A Textbook of Physical Chemistry Proof of Condition (3) Proof Example 2.4.1 Solution Thus E, = a and E. = a, ie. no effectiv occur In other words, if we want an eff xg must be nonzero. This conelusi ‘maxinur: overlapping, theo For example, is antisymmetrical (pos lobe onthe other side). Because of diferent signs gral Syp has «zero value even though the two orbitals over shown in Fig. 2.4 2, pa Hence, no mixing between such orbitals can occur onic charge densities bn the two hydrogen atoms of H molecule the values of C, and C, ofthe ground-state molecular oil a ivea the zero- and nonzero overlap approximations. Giver: Sug = 0458 4 ‘The H molecule contain Ycecron. Thus, i the 2er0-verap approximation, We may @=qGeos Tus G=G= 05 =0.707 In the sezr0-ovecap appro G+ c.c5 9-05 2 scc5a=0s Since C, and C, be idenvicl in H} Decause of symmetrical nature), we have G+ Gases) =05 Theories of Covalent Bond 227 os * Troasea or Gy=0586 =0343 Thus, the yg is given by Vivo = 0.586 Vigan) + O586Viyn4) (One of he moleulr eb fa dime molecule B Yao = CrYisiay + Co¥oam) + Cot co tha an electron spends 67.0, 21.6 and IL. percents of Ks imei the oils Vig Vigan evel, deter the form ofthe 200 fancton Yq inthe 2r0-oveclap approximation We ae given that G=06m;, G=0216 and cf =o. “Taking he square fot, we get C)=0818; Cy=0465 and C,= 0307 Hence, the form of ground-state wave fiction ie Yo = O818 Yiu + 0465 Yc + 337 Vp) (Note Forte ground state wave futon ll te coefcens wl hae pov value) ven by far apart with a0 equal othe sm ofthe enerpes ofthe separate toms. We may est separately a8 Era Ey) + EG? e410) those of a ‘The above assembly may equally be represented by writing thew a. e412 Eg! veC2)) (WaCD)! WAC)Panay suoqeiou amp Su moog (ALAND 1a De +A p+) 1b arn annum 9% ‘pazewuou ar sjenqio oruowe 24 JL maa an Ay 188 om “(r'52) ba wary ON Jo vossaudxa amp SupMNSqAS (ORA19%A) Oe Beaman ~# uossoudyo am 4a poppe 29 uo ABU a, %y 115 81g wt unoys se scoop suasaxda y pow Yr sous 24 so 622 puog nu2}9403 fo smuomL sa Og = A woRenb3 ss6ujposyog, sf voyenks fupamps au), + 0 UorsBeLdeg 0 +g = 0 8 yossuny OF-OVT 99 H UNS ein ap anu ew ag pon y se Fay Jo se usta “ioe want 20 30 asd FeURHO JeINDe}0") Jo uoissaideg ‘St vonsaf9 200 pe suid ows surIUGD YoIyH Uo! spHoafoue MBRospA aL, {H 40 LNSWULVauL ON-OVOT Sz ora « iva AD FMM Ly = A atu 2 ‘sg “ore 0130 ore ose Bunjq suONZOS sen Hog SFA senna ot a of Bpoodsonn9suerean ae 2 pou Uo Paso 29 er (p12) "ba won se wonaony ane a4, "wef 200 SHIDO Woe eptog yous se samnswoqeoo asada (172) ‘bal SUonouny ann au YACNA J = 7% aon ‘Popam voneHes Jo diay yun pouraserp ame pur ‘> sesu09 eu ACTA = WMA suoruny oj2ua2ap ona ore) 29 Jo vonsutqwoo seu opuory pur s9p9H “s1n200 uo ‘wows paeosse ag 0 parpstos | uano2> aay YoRUIwOD YN ake Sea 9° wonceo wy 1 vox yodnsp ouDe om 4}801 asp ate SNE oma 9 os ng (@IACD)MA =A 2 Ory? He) vede Aion stoR Jo $e moja sey wors%6oxoqe amo uonoUny ae apy APS a PON A rye) EHS we a ( weit) (oe ug } _ AEE | + [AS A ay waif yo sreiedo wermonrUy] a, apo UoED HAN ‘yar 8% souesp os aon B09 aI REO =P EN BPSICD ONL a+ d= (OM Hin) + seuoooq uotssaxo anoge amp ‘pazTemnoU oun ap 200g Ausyucye oarskyg fo yooqreay V- $e230 A Testhook of Physical Chemistry Optimization of Coefficients C, and C, We can write Eg. (2.5.8) as pe Gt t Clty #2668. GHC HEC ‘The integral Fug is known as resonance integral, whose value isa measuc of the exchange of an electron from one atom to another. It always has a negative value. ‘The integral Syy is known as overlap integra, and is a measure ofthe extent of overlapping of the two atomic orbitals. ‘The coefficients C, and C; in Bq. (2.5.9) are optimized by the variation metho! ‘To make the energy minimum, ve 3E 29 ang 29 aC, To determine AEC, we may write Bq, (2.5.9) as BCE + 8 +26,0,5a)= Chay + Bey +26,6Py and then diferente respect t0 C), Thus, we have FOC, + 20,55) + G+ 26,65 pg) @BIC) = 20,04, + 2C,Puy ow ) = 2a +20 yy ~28 3g.) ~ his C+ Can B(C,+ C5545) =0 Simi, evaluating 360C;, we eet CPaa + C85 ~ EC Sup + 2) =0 esi uation (25,10) and (25.1) may be writen as C\(@4- 9+ Guy B5)=0 25.120 Bua F545) + Clty ~) = 0 25.12 in the matrix fr, we have MB Pas ~ESy, Pro Bu y-EB Theories of Covalent Bond 231 @s.19 [Expanding the determinant of Bq (2.5 (04 = EX a ~ B)~ (Bus ~ E Sy @s.13) quadratic expression in E and, in principle, can be solved forthe two roots of E. These roots are then substituted in Eqs (25.12) to get the expressions for C, and C, foreach root separtely. The numerical value For the hydrogen molecule ion, the problem is very much atomic orbitals which we have mixed ae of identical nature, It BhCao 5.16) and thus Ba, (25.15) becomes (a8) = Bha~ ES yp" =0 © @-B=2 Gg~ ES) Hence the two roo ae sim esi) “hese energies on substan in Eqs (25.1) sve Cyst Cy (2.5.18) Hence, we have Yewo= Cans + Wit g= Sthe 25.99 = obs Veo™ CMa Yi p= the asisy ‘where the constants C, and C_riay be evaluated by applying the criterion thatthe rolecular orbitals are normalized. Thus, we have Hs) = 1 or UL #14 25y)=1J uoneye4s 2430} IROUUY 99g 4, JO REN TA aay OH 39§ ou cagz= nceit uz S222) wane aid 75 =o 09 1 ‘mos pap a seb sou, oq ut aos pu sviey at paved ae sahiaus ayy Stan TEM paar us passed ty aq esd (y ~)dxo (Seer) 1h) = BS, "10289) ep eso oy 9000 + =| AE logy = (ses tare y+ = 1) 4» Gem =P Josay = 6 vom ‘eon ag Summpno wa poe %s pun yo sans au omy FunTNGNS (exo + = ‘anny an sun oo UL (esd) cvmtg = (Cae) Nera wr ‘among (61'S 2) ba wan sey pun“ shaw a (E22) puR (27ST) Sha IAL eso “seseaputsofinn9 Jo 2200p amp se sosvatoop 1 pu Bou ous om) 248 sfenqo om 2x voy ane St ane 2p pony sjenq0 amp yo stone aanea emp uo spuadop ose epranseus say "uonsonb ur sjenqu0 aq 30 dono peoshyd 4p wo spuadep y Jo ane MN “sud ona sapeou sey pur g jax! wooatog wors99 Jo a8uENDID 4J0 90s aos siosasdxn Bupgeads Stor se yoy ar4ox9 se ua st pe 2) _lovmigy ay ‘ Sq vont st y amy €€¢ Pung n2po.09 fo savory ay , Wy) Wey) was (ee) | Te | tae ett = coh 8) = uso Sq cea) 7 ww ay), expo stsAleuy yy) resfowr quoqnd ap Suma sees angen 4p + Milly 2 %p A) + (a 289) ly (auy) wae |, Dg ett lomgy = > ae) SuPeay) Youn) Poe HA) = Yo oey am 2 2 poe atoms AHIMA) =o p "2 wos Aquos 5% waa, omnjosishyeuy (@s—vat 7 00 98 oH 20) “Dao GED am KTS Ws: =o asspucg yorsiyg fo yooarag ¥ TET234 A Textbook of Physical Chemistry Theories of Covalent Bond 235 Comparison of _ Comparison of ens and E_ maybe made by making we fcr Eas (25,9; orbs (2324), Fr simpy we may assume, Sq = 0 Frm Eg (2519) ba B=a4 By Baa Buy Since both and fag a negaive, itis obvious that {nis rial conutbues towards mang te molecule ls stable Beck. 252 nH, veo the bonding molecu xia whereas yy isthe enibooding that i, the molecular orbital yo has lower energy than Y-yo- On comparing eet and E., we find that E Bray {be conclusions which are identical to those of Bgs (25.29), "or the dts, seo Tey Yourself Protein 2.8,© o o $s are ONS A pur OMA Jo suonevasasias ayy, Texqu0 Burpuognue om 098 we vous ABsave fenuoIod wl osraiou UP sino aM SMM UE 1920 Buspuognu ay, Jpg Humpuog 2 wt Baa Mo} 30) {Bou Jo aseo]at uonoeie sty, anyea aanedou 1 a2 ‘sm, "Uo]ndayseojonu oy uEy 3 28] sey uonsem 3t ap a4, ‘au Spay yo Aaygegand yp re Bupeaypay uso smadde yor A"A7 wo om HA oNpOH atqeradde aney (24 pus 14 oq ayo ont amp UaeiAe9 tor se-e ese) waa; =< e+e oo corso ra ae amy 2m, Lee prog uoyoney fo soz OFA pe HA (g) paw “OMA pur OMA (D Jo woRNSaHEDE OREEEID SST"HT uuonniog bez woraoud ‘panoadsas O""A pue ONA sjeigio sensojout ayant parerosse suonnquasip Aujqegosd uons9j9 om wosasdas OA pe OA sur ous, S57 “St wy UMoYS ame oA pue SA B ssou, (0°14 poe Fut sqenyo swore ow yo uonoengns pur vowppr olga ay) Jo woRe.Uasaidoy Bunge Sydus & uwsexp 2q ue> OA paw OMA yo uonmnrsandos omen’ ayy, eoqudes ot oma poe OA yo S09 991 sao. josuon st oD Se BH = we | | ae assrucyg oorsiya fo yooanas ¥ 9¢z238A Textbook of Physical Chemistry where = (Vig Ha Yi.) (Yn lad Wi) (Yi a Pa Bum (Viue 552 (Wie or linear struct Bg. @) becomes po GAGs area +ccyp Gade Minimizing £ with respect C,, Cand C, (ie. subsitaing E/AC, = EMAC, = EAC; =O, we get te tree seelar equations Gla B+ C,8=0 Cip+ Cfa~B)+ Gfa0 6 a Gh Gla- B20 6 Winking Eas (4)-(6. in the determinant from, we get where = (a~ YB. In onder to ge nootivia root, we write x10 iat ois Ths xG?-2)=0 which gives x= V2, 0 and J asthe three roots. Substnuing x= - 2 in x= (a EVA, we get Ex atip Substiatng the above expression in the secular equations, we gt Ci V2) + =o C/B+ CK V7f)+ GB=0 Cf Cf- 2H) =0 From te above equations, we find C26 and Gc, Theories of Covalent Bend 229 Substiing these in he normalization condition Gededet 1 west C= 4, et G5 and = 4 ez 2 ‘Thus the molecular orbital ys given by 1 1 Vises Fant (bonding) 2 e 1 My PY Ein ar vB Proceeding silly for oer two 00, we get 1 1 Ysa Jp Mies Ys ure ® (content) 1 Yao 3 Mat) Fe Yong + Manes Ema WEA (eubenting (i) For equilateral tangle structure, we , G) becomes have Sy = S..= Sex 0. With these, G+ rar 26e +65 +4608 Mininizing with respet to CC, and Cy, we gt C(a-+ G+ op=6 Ops Cha- B+ Gp=0 C B+ C,8+ Cha-B=0 which i oe @ NGM 2 =0 The tee rots are = 2,1 and 1 Subsitutng x=~2in x= (a~B)/B, we get Exasrp Substiuting the above expression in secular e C(-20) + C,B+ Cyp=0 C B+ Ch- 20) + G0 C+ C,8+ C-2M=0 ns, we get(mas), 10M M4 ZE8SH21'AS SL p UE (parea>, OW PI BL'SEE >T'A® BFE 1 yenba sinoaiou vafospxy ayn Jo Baus puog aq) 18 om ‘swore woBoxp4y ont 24 Jo ABsaue ou) paneajn St ANTON oxy yyy "wd UPL ue Jou HX 80'E-) A2 $6'1E— ae sone PONLasqO nnoedsad aL “ud Ey 430 ome Jajontaye 4p (JOU FH 96° ~) AP 8V'OE ~J0 MULTE KBrOuD [eo seonposd (5-2) “ba wt (e9'2) “bg J9 uounnsqns aoreIedo URUOY dy uso woiindas uasoojo-uonsayo 40 e5na00q suoHEodwOD 1 seanposd 2 uy suon2o[9 om Jo souasaid am ‘hata Jo yjod aanexnuenb © weg (@*A"A\C*AG)*AY ee Torayanieraoray 7 Suu nen pou 9 Ro Wo 0 a4 90 SEV iy. 15 an an pom ae oa an os e92 OAD «HA Ig 1h Jo wo} on aye 4 “A uoMswEYy OW-OVOT aH UL estore -oeenay aa (ACA SA ay woo 4 sg 4 van 9 pu sunray ‘ds pus yeeds ap ynoq aprjour 8 uopoUNy axe se|NoaoU feos ay suds aso A gto so2youSupuog8Ho] ap Ao00 a SUONDSE OM EL 19°2 Std uF uMoys ave soouRisp snouea amp slay era) | Su(POuH) Soup) _ 2 é@ 2 Stony) "°244) (92) We eg mopoa0g jo sory q voas8 s sowsado uerweayerys, ssazurds oq, ‘suomso[e om) pu suoyoad ow) suryuo9 ajnooqour weeps ou, INOTION NIDOUGAH V JO INSMAVSUL OM-OVOT 97 THC poe, Hump ages anus fy a 80150} op omg Ye +77 = CHa + (Ha mI EN +00" (SH) THE poe, ump ages a. st Fy eu] OM sp 99 1 oun} ap suis 7 = (HZ + (Hz ome zpz +z = (SANT HE omg oyae ow 1d > Ca soms me = (Hela poe ges +oe= CHD () O) tg > tg oq ey ann ha pounds wonbesues) ‘TeuGH0 Bupuoqne ap asad oo st wonsoe 9 “Hu vamanns aust reread ayy x0 poneyaid asm seu oy Soup ‘amonns se Jo a9 9tN UE SE BREE mj a 9 pow e sow yo wt Knewoed wun ip tt nfo Samoans ayqesn We sa ‘sua 20 Yow oan ae so Om arth SIMONE APMED [IES ofp We sono oro woH ede sj 2 paw tore a Jay oA PHO SHU wonso Mp “smcuy age 99 01 ps0 wy 7A 21) 2 par x soon dsr Butpuegnu Spry ego ue UF wWasod 51 uonDoye ao ‘amnonas ojBueuD feraepnbo Up (q) Gp ei smoyos g-vae%y aI) 54 say y = pe Lory 138 an "vompuo> uneasy a wos Q-='9 poe o=% me fou a ‘spo oo ane ees pumas? 2 0 oU EAR. aN pj ap JO sn SUPE 085 49 +1 soni suouenbo spas w Bun d-o=3 uy an | = 1008304 @upa0) eae a ona Coenen tS ce x0 a Sou § . Bageney T 2x wonypuco wonerrmubod ap 1 Sonminsqns Uo orga 925-9 uy 2m ‘sorenbo ahoge ap aH Axsspuay jorshyd Jo yooaer VOL242. A Textbook of Physical Chemistry ‘The bond energy of H, molecule is larger than that of Hi The bond dstani of H, molecule is smaller than thet. of H3. These values may be interpreted in tm of more electron density in between the 130 nucle 2.7 VALENCE-BOND TREATMENT OF A HYDROGEN MOLECULE “The simplest wave function in valence-bond framework is given by Y= Vie (Df) en Expression of The Hariltonian operator ofthe hydrogen molecule (Eq. 26.1) may be writen x Hamiltonian Operator Hogs H+ Hy 7a Bia _e e where =~ Hyp We Bein” GR” Rig n=- A vt ain wee? __ ty, Greg” Gnecie * nein Green a Expectation Value Assuming AOs are normalized, the energy of the wave function can be evaluated of Energy by using the expression E=(yldl yy 273) (On substituting Eq. (2.7.1) in Bq, 2.73), we get E= (Yay (0) Py (2) [H+ My + HL 9 Since Wig) ad Veg) ae the normalized functions, Bg (2.7.4) reduces to Eaays+ O* 2Eyen + O e15) H’| vy, Expectation Value Energy Theories of Covalent Bond 243 On substitating the expression off, we will get “The integral can be evaluated and is found to have a negative value. hydrogen molecule willbe gives by |) 2600 = 0 276) The binding energy of Frig = ‘When @ is evaluated a different values of rit is found to have a minimum of shout 24 KI mol”! at a distance of about 90 pm. The expetimental values of binding exergy and bond distance are 458 KI mol“ and 74 pm, respectively. The agreement of calculated value of binding energy with the experimental value is only about 5 percent ‘The above-mentioned poor agreement is due tothe fact that itis not possible to label el vit lection 2 with Hy, Itmight be posible that electron with Hand electron 2 with H, Heider an London incorporates this the molecolar wave function Wo = CVia 0) Mi + Co Min 2) Yin Cl) ean We write Bg. (27.7) as | yi (2)wed -2 ve8 94 (GT2) ba wa 30 wossouno ap jo woRTANSGRS a SERINS avo be! 1 an ‘uotssudeo sy BoE HO (a841 ple, , (2841 yt o= (,s8tt-glo+(FS-2|0 (Sore i \dvo") yo om “gre2) ba ug yo wowssxda ain SuTMANEGS 1 Stl ora . wae Poa amg Jo s002081 50 . (st-)F=9-P sons 0= 89-9) 2?) og seg pw 1 SUNN, wal ey odo feat a TPUGIO -yuoye oz pue 1 suonoaye yo wooo Jo wondaox2 ays SHO aOR JO 2afy anes a anon 8d ar Ap 'A saonouny a '9atou UeROIpSY 20 paygduns 51 (6102) {9 pue ly siuajayjaoo ain yo sanes sap sapinond BA wonders ea aip Jo uonezrfeuiou oun yi Buope suonenbo mynaas up Ut porns Uae ‘001 asa 7 J0 S001 omy sopinoxd poe ut nee st I'L) Poh (red 0 4s9-"9) -(a 0a") pion syorurmsnep aq Sundog iuounuzrp spo se UOT SE MEHTA STL sae -sa-"9| @reo o| wa-"g a-?| 1s ai ‘suorenbo aon jo suoNnos Tta|OW any oF 39AI0 UL fol] ate sa~*¥| arco voll saya 198 om “wy xe 4p “pion zopoar se Uoory ame suOHENbS 25, ered) 0=G-*a)9 +Q59-"'9 wren = (sa "90+ @- 9 She Puog n12]0409 fo sou034y ‘9 pu 9 swopoiyeoo. = yo suoyssordxy aco nym 99 Kew (p1'L'Z) poe (EL'2) suonenba 0-6 +0199 +9 Bam O= DENTE Mead *ApreyEUNS 0= (8% + 'o)a - Mya + 9 5 a onto be wan aso aT BH HO __soxbrb _ be Wer bo aes Re * ae son stg Yyor+ woe = (s+ +b) (2) 44st + oF ae) anrB 011 on ods sp ue. tyoiot+ wb +b =(s0!0t+ D+ DIE sv (Z1'L'2) “ba amu am “"QerTe stENIeAD OL, e be o- 22 pe = 22 ae x swuojouje09 vps on % por ly ormodsa nya y umm oy jouoneznundo S++ wooerwo+ 95 =a se (11 C2) ba ams weo om Bg =O |x| t= CA |*H| 4) w= |*H| 4) ‘ywosandoy -sBany depaso ain st aun S=SKS= GA | wea) CIA |HMA) = sar) HOA) = GA) letxte Omg) = Aasquoye porskyd fo yooqreL ¥ y¥e26 A Texiboot of Physical Chemistry Theories of Covalent Bond 247 Note: The fact that C; = + C; follows directly from the symmetry consideration of hydrogen molecule. Both the atoms will ave idetiel charge densities and thu GF = CZ. From this it follows that C, = C, ‘The constants C; (or C;) may be evaluated by using thé normalization expression of in: Jvinde = + 42G.G87=1 Substituting Eqs (2.7.25) and (2.7.26) in Eq, (2.7.20), we get For C, = C,, we get Cy 2223 b,x GB, CEaan +2)* QE 9S? +4) Ra G.=-cynegt G2 pte aay 18 ns eas = 2B yy + S44 72 Analysis of won Inte 2 nam (QE, + Q)—(2E vay S? + A) 1-8 27.28) we get Greig Greig Cree (2725)sesmonss amo! said fam) sues gU02 0 ayn paqunsep se samonas 2p wosanox say og 2p oso ahOgE (see acy moa scormmacyrrora] SAVE arma T yo am uopssaxdxo anoge 2tp ano Sumsodo rsa) (s+02 1% Jo vonouny aan pores ayn ‘sm, “A pause axe suds misoddo ite su0399p9 ort “H SNNOTION N3DOUAAH V 4O SINAWIVAUL GA GNY OW NABANLIE NOSIUVAMOD 87: ‘uso 2d gy soe sowoony ("gw wotsase a, Meanoedst wd ypu 188 ‘papnyouy ane seaman 210! 24 301 “qu20 30d 0g mnoge oF paowEyUa mw Pf S96 5 paurEao snyes UL mon Bury Jo peetsat steamed ajgensen ap se Z Sunean “e [PE 98¢ am000q 2 pet ‘pao mes tsp 9 959) om 8 pee ea, t a a Mt ft if | + 62 pow moyoso: fo suo lew PA ZERSP pow wd pL ae ‘oge pares 58 sonea paatoqo a Jou PY Soe = |°a'V] sm weg 7 sn900 anuno 2 snsuan ‘gy Jo unum 24, 4 Jo samen tre we agersun sp “ay Seta sure uSBaxpAiyporeost om a JO TA ay ang pug yeoruoyp ages saqunsep “ay Yep snot ‘wos se sxano ap 9 avo “1 3o sana snouma mp wurede pono say UU, St. vio 4 ons swore ueBospsy om 0 anes oxjow uakeapKy Jo ABO ou, acco a> ta 7 ‘Wim ue anpeRou asow 9g on ys samen aaNAROU 2804 “soueprpseyonusaiy payso5qo peop povnyeas 99 UeD V ue sTesBoN a, eyao se1nse1o¥ jo uojssasdy opts si Sian) | “ay pwa Tet «ora ds-s¥ (evo Sou) Ausquayy rowstyg fo YoosrRL ¥ a¥c250 A Textbook of Physical Chemistry Method of Configuration, Interaction ‘Second and third terms The ters at Yi ‘These configurations as nt covalent srctu (2 one eletron to each Bf the atom and hence they Since the coefficients of all the terms ae identical, it fellows that MO treatment ives equal weightage tothe ionic and covalent stract bbe poor at large internuclear separations since the dissociation ill be an equal mixture of fons and atom. In actual practice we get two 4 Inydrogen atoms. On the other hand for very short internuclear distances one expe, that there vill also be some chance of finding both te eleetrons inthe sane atomic ‘orbital. Thus, MO treatment does take nto account this fat, but perhaps gives more weightage to this fact dhan what actually exists in the molecule, ‘The valence-bond treatment accounts for ionic structures by including the ionic tures to the Heitler-London wave function which represe structure. The amount of mixing is determined bythe variation 8 value of 0.16 as the coefficient of ionic structure, The resl lueatment has been modified by taking orbital exponent asthe vaible, The MO can be improved by the method of configuration interaction, In this, the ‘wave function is taken a linear combination of functions arising from different clectronic configurations. For hydrogen molecule, the following four spatial wave funetions are poss Me signed to the ground state molecular obit jgned to y, and the other to onfguraton interaction, we write the improved wave function 8s YEH + CHE Gist Cay 8) ents ate determined bythe variation method ) canbe simplified by considering t 5s will mix which have the same symmetry with espect exchange of th wo protons. Remembering that y, andy. are symmetical and antisymmetical wave fa the symmetry nature ofeach ofthe above configurations can Hs, (symmetrical) (aotisymmeticat) (Gym (atiym), (ym) (antsy) Theories of Covalent Bond 251 (antisymmetrical) (symmetrical) ‘The functions yj andy, ae symmetrical in nature whereas yh and ys are antsymmetrical. Hence, the conigurion y will aly mix up with the configuration ‘yj thus, Eq. (2.81) reduces to! VEC + Cam 82) (On opening the brackets and rearanging, we get W=(Cr~ CD Yeonten* (Cr+ CO Yc 283) negative vahes, respectively From Eg, 28, of covalent and ionic structures inthe In one ofthe refined mole be larger than conuibuions ed molecular orbitals become uneven. the contribution of covalat structure will it follows that molecular orbital theory with coafigueation the same as valece-bond theory with ioni tenns included included in VB theory and when more and more of excited-state configurations ‘ate included in the MO theory ‘The MO theory is mathemati h sirapler than the VB theory. The MO theory can be applied to large molecules easly withthe help of electronic computers. By equating tome of the cumbersome integrals tothe experimental quantities and empirical parameters the MO treatment to larger molecules has been very much simplified (See Section 2.16).Imrie ammone —_woneuqweg NaN ‘tonnoadse ‘g"a pu dz" ‘sz’p a poreulsop om snp pue anew w apensin ame dz exio Butpuog amp poe 42.0 por S740 sTmIQNO Smpuoqnue au}, ~sfoansadsas“Sc*x pu dzto ‘so st poveulsop ame sn pu same ve apes ae dx eno Sexpuogne an pue io 7 ig ur ways SGI sqNAA|OU 49 sweafep moraoo a woly “aduosqns ap se (JexmouULXSun 30 ppo 25 pom ‘smu ysuejse Ku £49 you op sjenq30 Suspu0q ‘2 uo suaise ue Bupse\d Xq poreulsap ame spenqu0 p04 ‘imo si oy oadsas yh 10 poteg pojfaqy| JONI st uoneUBIsap yenqHo axoge ou £2 Puog meqDs09 fo souo2ys ste ‘anuao sy [eg ap Jo Ainamuuss ayy 30 sa}eYD Buypuograe-ZurpLOg AHL sjoquss "gu ‘4 wmoys st seysousop jrxqO F[Oo9TOU HOT ‘ouestp oo] aesedas Kom Yor oH o @ xo ae) -moyea Want st Jo amen aun wo paseq sprygno Jo woHeURISSp aM, oua8ep fiqnop [Te are ouestpeaqonuony on Buoye nveMow sE}sueyeyquo xp Jo UeUodICS ay ‘x major fn Suoye wusyuawou mndue jug ay Jo yaUOdwoD Jo anfeA BY (1) ‘sony Buyuonoy m9 wo poseg s11'67 AGEL JO wumjo> wet 24 wH UAOYS UoRWUBISOP 24), ecu mds Supuog| de'uodzax ———apuoguee d'or upg ke'ow0ée.o ——_Spuognne xbox smpa0q (0 AW romeo ‘pong (AWN oa apwoane onan ao soma 0 bupucg oreonen 7 JequnN wMIUENO Tedjouizd fo SIeNGIO oun wos POLIO} ‘Seynosjony slworeig sPoFIMUOWIOH Jo SIEUEIO JAIMOOION VT IaEL ‘6 Fig OF UMoys are sodeys ou. (167 A198) Fumpuogna® pu BuIpuoq “sjeUgIO zyR>oIOWN omy seonpOAE 19 Ye NH Kgauunds 9 anp worenqui {ve sonpoud you op (ow Jo voneubisoq sreyaio s21nd910W je sadeys, ‘S3INOTION OWOLVIG HVSTONNOWOH 40 LNAWIVAEL OW 6 Aassrucyg porting f0 YOURE V Te254 A Textbook of Physical Chemistry without s-p Interaction Fig. 292. Molecular orbital energy diagram Theories of Covalent Bond 255, In terms of g and w representations, we have © GIS < Gils < G26 < G28 < 0,20 < ROP < F_2P< C20 ‘The relative order of energies of various molec ‘be osbitals 25 and 2p have energies close to each ote, Because the positive overlap between 2s(A) and 2p,(B) or vice versa will also ‘ter words, each of and 1. 29{8), (i) The extent of overlap between the two involved orbitals Since the energy of that o15 (or 6518) and a1 (r 615) have energies lower than molecular orbital energy orbitals has lower energy than 2p, 28) ies weniently by mixing 02s {6 o2p).Since the end to end overlap between two 2s orbitals or two 2p, . and 02p, and o¥2s and o*2pas described by the following wave functions is larger tan the sideway overap between two 2p, or 2p, obit that the separation between the bonding and antibonding ' o the separation of those of ¢ obial = C029) esa) (o*2p) 292) Wa = C02 Was Cy ‘These interactions make os and 92s energetically more sabe, and o2p and (o*2p less stable, i. the energies of o2s ard 2s are lowered wheteas those of ‘o2p and o*2p are raised. These energy modifications are shown in Fig. 2.9.3. the above facts, we may draw the molecular orbital energy diagram ax shown in Fig. 2.92 on = ni =» a ot e293. Ineacton oe between 02s and o2p, fn o*bsand "29 om oral | Bone = For ligher mole, the above intiacton ae important. Conse i enesgy of 2p oti becomes Inge than hat of 2p and thus the ol | = echt exergy dagzan is motte os shown in Fig, 294 | From Fig. 29.4, we may write Gls < ots < 02s < o*2s< Mp < o2p< HID < a*2p pene wwe have In terms of g and u represent om lee tee a i Gls< ails < 0,28 < 02s < 2p < 0,2p < nlp < 9,2p senate ‘This order olds forall the frst row homonuclear diatomic molecules except Q, and Fy, 2.92, we may write GIS < O18 < Os < O° < Op < RI < HYD < orp g 2senor i uy suonoajepasiedon yo souasoud ay on anp st ouesqns © ur wsneudeeI oyges 859 sear pexq30 Furpuogne ap uy EN SEY ‘ges sxour anoaqont ay Soe eign Suspuog 4p ut waN29po Ue Yo VOMIPPY ‘suonaeyo Aarpu09 Jo ssooxa Toto jo se 240 st anaofou# m 29psoplog 30 spuog Jo JaquENH ay, & jour iy Jo ABroue wom glo urpuoge so 2504922 ‘29 uo sposdap pang e Jo quan aU, & anny om e198 wy ‘p20 ypfuans puog ag s9BIe ‘Buypuog wr suon29,2 40 s¥20x9 ° ° era ee erw eel oyeom mot z seer vest z , zor st s rs ¢ 9 ce mst ‘ ce mt ’ ress on z cars set ° o - we z oon ° a - ws 1 zerscose not z exer so 0 1 “wii dapuo tucsnye Bunpuog tog pig fo st3o9 HL ‘Seino9joH WONG HOFERUOWOH 4 JO SYONEINByUOD qUOHIDAIR WaMOT SUL TET Or 767 aR, UF Bes ase ara, “sor axn}sod saxp Jo 240s pe yoy 2 sayD2]out stuorep 2pnuowiog Jo suontanByuo> Suan op WAOP aIEM Mou KO yA ‘padnaoo Anny sue sous an Nog Hp SuIMEoUE “P49 -(S140},510) ‘eur 9 aoupy wep jou Aue Jo vor yuos om sn, Supa ‘2 u ata Kom se ewer St puog meqos0g fo smu034y oe wnoafe Ou key ode fo sey rod K2o4 © BuUpISUED Yo 1 soonparwoHsssidxo oxoqe ‘0 one es Sn PI6Q eB I} usON EO} O} = $09 NON 298 om [4.0 pues]. Jo suossandxa ayy Jugmsqas 02 + L610} 5 na anoge amp 305 ‘s9inooI0n 2 ‘1U0N}9913 a aursgo sdzpursz uooueg ‘wonee=01 90, aroun uate mga MOON FETA asoya moi fo yooaren ¥ 95t258 A Textbook of Physical Chemistry Problem 2.9.1 Solution Keeping in mind the above characteristics, we may derive the following conclusions regardiig some ofthe physical properties of diatomic molecules listed in Table 25.9 1 The di { the fact that H, contains two bonding electrons inthe Gyls whereas H contains only ‘one. The decrease in bond length from HHS to H, i also due tothe above fac. not sable in the ground state bonding 61s and antibonding He, however, is observed This is de tothe promotion of electron fom antibonding othe bonding 4. The Be, molecule 5. Ne parmagsic bn the maximum bond dissociation energy as it contains triple bond 17, Ingoing from N; to NS, the bond energy weakens and bond length is increased, ‘This follows from the fact a the elocron removed is fom the bonding cbital 8, 0, molecule contains @ double bond (one o and the other paramagnetic substance, tthe wave functions ya and. yy a8 described by Eqs 29.1 and 2.92, spectively, are equvalentto the molecular orbitals obtained by mixing the wo hybrid cits centred on atoms A and B, respectively. Substituting the expressions of 2s and 2p (Table 2 wwe get Theories of Covalent C= GN and A= GIG. ice Cis greater than CZ Yeon ude mor cotiios fom 62 (eC, >G) ind ao ere sa han 0° etl Forde incon yy, we have {tna = Vipin} - G {AV 20) + Vanco} "2p (ie. > C,) and alsocord (aysry- (ae =(a'es CoRie= reve yet am ((+ | -)}-® 7 We t. pure dz. 01 pazeduioo = 209 yedtoupd Sa Jo eH Op ami a 9 ipa ray 3) Won some 6 19¢ puog suapos0g fo souoous enue pusakqedso Zura: pu seotqu0 seqmoqomdz 0 ovsz ojo Suu 1 pautegesenaa0 Mayo (o2pKyy fo yoogweer V o9e262 A Textbook of Physical Chemistry H, molecule Het species B, Molecule (Gv) Ascerain the value of total spin quantum umber. From the values of MG, the value ofS, which is equal tothe maximum v ascertained, A few examples ae "5, end “1, ‘A FEW WORKED OUT EXAMPLES ‘The molecu electronic configuration of Hy is ( Mem, +m, =0+0=0 ‘Thus, we have Mgam, +m,,= (+12) +6 cotresponding 0 My = y of spin, 28+ 1 = 24 orbitals need not be considered as their values of M, and 210. For distributing two electrons amongst four spin m1 m=-l Values of m= 12m =I M, My O ao L Theories of Covalent Bond 263 lowest energy may be constuted bythe ier combination on sos A and B, respectively. Vaso = C1 ¥ise + Caine ‘The eneray ofthe otal as wl canbe detemined by eplying the vraton neti othe expression _ Yul Wn) Wrso! Yo) Gy (@~ E) + C, Gua ~ BS qx) = 0 ©, Baa Sun) + Cy (04~ E)=0 toa no lar determinant ost in E.On solving the later, we g secular equations to the energy of one of the ol of atomic orbitals and the other energies of atomic orbitals obits. In general, the two energies have larger value than the larger ofthe two In general the coefficients C, and C, are different and depend on the diference in energies a and a (or dit the bonding otbitl, value and that for the antibonding electronegative atom.vee ge FT eo 09 Fea FT, almp oanouye= t= yeT sun Hs sey aansod ¥e0= 990-1 9mm] RH 90 = S@c0- oc¥O= wow F] wo afm a, eaco= srr + san = (Oe 10+ stco= OH ‘O+sIzO+ 360= Oe ssquiu uonjadod smoot at (oes + PE A(oR2) = rte wessep on sepaog rit A = EASA gory PegvOnA LUS0 syenquo 4z poe 9g ume z jo suonoey sqpeus sp penqzo sf vaBospéy Jo pesodusoo Ayeeut st woosphy 30 +0044) img 0 roxas oe ao amie eno] a TAU c Aw UAT (tas DTDs Fes = TRAMMAGICO — SHUT “seuqio snouA yo s21ZsoU9 Jo JopI0 OANTTaH 9 1qio Fuypuoquod se wAOUN ase ee Suge wong paooyeun crew! sabe men sng poe donEguo> far or 210 z (sya) es © 2h 2 op sfeng “ag pur az eu “ZO pun £9 "9 ‘[enqy0 zejoafou ax 200k Sn ry song "ypu 5g pq im soem wszmpSH 0 HOST HET OpHPAH WHIT AH pue FAY saqnootou yp Jo svonemayuon UOR2VIo of MOR ‘aoye sso ap J snqv0 dz pw #7 is TE HOE MNgIO 2049/0 sugquos wore uoSompsy th," et dumx8) es98 2014 query aaneSouongoye atu) Haq an99]Ou NaDOUGAH SI SWOLV 3HL 40 aNO aumoney Poquosap s soynaaju naj» Jo suonemB4yuoo ruas29Io amp pI BoE saOE TCD ou axoge ayy 40} sfengyo seyaazqou SnouEA Jo sex#19u9 Jo J9pI0 OANETAS 2, q ‘9 ‘ON'ND ‘ou ‘Ne apniou soydumg‘sfenqio souoqea d pus s urEco swore op OR, ‘na TOR ‘HE pn Soydure STE Pouoqea d pur s qnoq streido2 sowyo amp pue UeRospAy st swore om Jo 2U0 (*) ‘Sanur sry sngo0 ose wo senqno “dz pu sz Jo Bupera mp aout pue wom 08 ue op SonesRA fy HTT 50 sons ao au HHT OF tou 1 spego dz pue sz Jo solioue so 2ouareyp ot 'S0se9 38048 Hf S92 puog mep403 Jo souo2yy sang posing fo youn, ¥ WE266 4 textbook of Physical Chemistry Hydrogen Fluoride Fig, 211.2. Correla ‘on diagram of HE Diagram for AB Moleet Theories of Covalent Bond 267 4) and 2) conrespond to — 110 10° en, —374 respectively. The 24P) orbital energy is much lover tha that of (4) and that of 2, is closer to that of 1a). may be assured the. effective combination takes place only beeen Is(H) and 29,7 bits. The i Figure 2.11.3 displays the relative oebtal energies in AB molecule. Figuré 2.11.4 Aispays the boundary surfaces of some ofthe molecular orbitals ofan AB molecule. om, “Ey i! =r e on a = “Thece will be one sigma bond and tee lone pei in the thre noubonding : ‘This arrangement corresponds to the Lewis soucture (H—F) ° tom A wmoksie som ‘Table 2.11.1 records the electronic configurations ofa few diatomic molecules. Tabi ‘The Lowest Electronic Configurations of a Few Heteronuctear Diatomic Molecules ‘Number Molecule Elecronie Dissociation Bond Bond ofsaence configuration eneray order lent econ iar Be s Bx (ts (m,,P(op) 3492 9 20 mo 2s BOTH ATOMS CONTAIN s AND p VALENCE ORBITALS na 7 Cx} sors Rp) 1866 Let th tom B inthe moleeule AB Be more elsctronegsive than A. The energy of co! anomie rial of ator B will ave a smaller value tanta ofthe coesponding cxbial of stom A, The formation of ¢ and bonding and anibonding molecular 0 co 3 cxbials ia AB molecule i similar to those of homonuclear tome molecule. The xo! shape of molecular rita isnot symmetrical. This due wo fact tha the coefficient ow ia of orbial belonging tothe more clecuonegatve tom has ager vale inthe bonding h So es as ts orbital and lesser vale in the antibonding obiaus ut vont a sedan up sp, "s2[po3jour SWORE FeayoNUOON quo se[noafors 20} wesFeIp vone|as0> amp sKerdsip 7-217 NFL reno Steptog ax Se saneypq 20uDq pue Wo engi Sonpuogge ae se seyoq wa poseatoop st wonezndsssofonu ap Se sesearoutpengno ue yo Asau> ay 3 Toque wryuen edad xy wy uEND A 01 *payezedas sn se soeeanop smiqio Jo CoB]re9 sty Jo Kav oy, pg por "pe “de ‘86 "dg ‘a aso oqUnU wwe edomd uM NSU 10 ogee soniposd uorsedas Wo Yor sfEnqio UIOE-POKUA -Zunpoog 2p aapsuoo sTengio oso Sm 2aquiny wimuenb yedyud ours xp a ‘Sayeop are om pu ‘swore povsedas amin pany st 28meyo seojona ayy 28n2209, se Spyde ssnaisn serixo Jo Aofareo sm Jo KB0U9 OU, dg "dz 5] foe aso] aqua wane fedtoud ones 2p Jo sfeiqio 24 Jo 04 ‘xp areredos ox pu wore 3 9PISUOD a id "pL Jo ajduioxe ayn BauopIsU09 HOM $1 “suonemoysoen sreudoxdde 211 ga2 0 poroouuoo am sfiouD Tory ypeosdde somnoue st a4], SHES OV'T 21 Bua] aati Uaeq ane 687 puog noper09 fo sau0%s J) sqeuqio spnsojom snows yo sorSious pe sodays sy a 01 aoueisp oe] © mos pufedoes ot wes} ojaojous oxen 0 Jou (2 — NM dsouog 3 oupyo uonduscog ‘SWIVUDVIG NOL TAUHOD 3HL ONY Ld30NO9 WOLW-G3LINA. 22 aos sjenque dz 20) suonsuny yeu suo Supoauyeopeuasaxdos eure 24 -¥ wep anyefouonD2p atou 51 wore fjoxom LY we Jo STEAL eRHDPo MH IO SdMeNS YT \(-) wre, SOO won sea enoorn4 wpemgneg sen ery Ausspuryy ywostig fo YOR, Y 89eeg 4) Dat ad ca od) Ta sqenqio dz pu sz yo suonemawoo 120m ‘Amory amy a paced sone] aAp UH ULINIOD YoHD UEYR poHEyPUN SURE (v¢12) bajo weep ay Aq uaa se uonouny axem an Ip UACHS 99 saxo Yow pV 081 Jo of Bu we ye powau exe pur ‘amEU WH 612) ba Aq won wonens 00") "A ‘a & poquosap 29 Kou w 4p ao Bunowosd q pour oq Su) sasoqou swoyEyps¥sjNvON 20 ETP HORAN pen pads eetcal ° €Lz pug mayosop fo souoryy, ‘poze Sem soto 94 204 pur “equ SE wow postu oan yn do 2M \ seq wow oyp py wow auo Dep Jo onquo pragty ap uosmreg Pundde|2H0 ap Aa. poured 29, Kew spuog pezieooy ay) Jo woreuo} a ‘eaNeUIOY yruvoysuen ponewoxpeas 5 pezteo0] ax OnuE xo} 2[ndofou Ua =. ero pezieo0fap are sTENGFO jw enone waD!IE9 spUO, syeuaio PuOAH youopeueldea STVLIGHO GINGAH bz sojozyom scyerp _$3}nOB}OWY O}WOREI yuoo oyuonao[a aq) UAOP aM 0} Pash 9q RDI PUE “ETC Fig JWa}IMUOIDIOH U1 0} pjs29[0W SWORIP 3e}DAUGISIOY 24) 20} UMETEIP UOREaHI09 at] we4BeIq UOABIA1OD “ajna Bysseus-uou oxy oweOU HALE se Z arowe pomun 24) yay syeswg snus , No Belt tending oC, sears ba a in bonding ori, te coeticiet of more tor wil be lager than tht of ies longa tn nei ‘is caseot auayoo A> Btn aa Rasoe pve aera sexy ? these A coped e208 8 a Relative Energies of Molecular oe cof hydrogen atoms ‘of bonding nature, Hence, its energy will be smaller We SE eT be a symmetry of Bel, we expect that Gymad C= Ce Under the zro-overlap approximation, we will have G+G=1 = wid=1 = Ge mide = Ge (n2K055" -o55 ad - G+G+Q@=1 + 2+G=1 = G= id 3 G= fi-2x06e = 045 Since the elecwoniccoatiguration of BeH{, (Charge on H, Ge Hy) =2 x 0.597 +2. 0.468" = 149 Charge on Be =2 x 0.55? + 2 x 045" = LOL “Mulipication by 2in each term in the above two expressions is due tothe fact that each of the two occupied molecular orbital contains ? electrons. In Fig. 2.143, Since there are four valence electrons cach HD, the electronic configuration of Bell, Example 2.14.1 The wo lowest molec wecim Vo= Cova Cs with C, = 059 and C, = 0.63, re a doubly degenerate nonbonding o ofthe moleculeseq sensoy pazeoojuow ony pousauen axe Kamp uy suo seraoyons paneso Jo soiioua uy aBeRD 2m SUQEPO OST SPIT aL a") #1 vonem yuo no} sey Tyo 2oulg wesBeIp uodefaH09 peroedxo ‘suostoq> 2ou5ye4 ‘sqenqio (e1e:0aop) FpuoaTe® o fom 9 E822, jenquo dz Jo egy wey sores 1 HG s7 JO. we puaiy so srRione ayy,“ Jo sTetqo pugKY ds jo uo! a Jos ges zou are sop vapy yo sTengo 81 9" Wty anneovonDo] 0m st FH ouig sone Hf puP oqo steno omen so stove sane 9 xe “T - ‘mop wont sds gmotog Ka ano pause aq Kets wip wosfasio> yo wononnsue> OEWAHSS AL, “gjeanoodsos SA poe A sTequo Beqpueqne pozTeO0 {nsofou pare] ost 9ROGE Nf Jo SUONEUINIO a FO~ 1-604 =A 1 Jo suedsaanos Suspuogn 4, ong p 2% 31 %A pu YA Jo suoneurguI09 9 peegno azo] oma ORION RD taxa 9q HED SHGIO PRZTEDO| O61 nso Jo USKUHAN AOGE OL, ‘au ‘segue pazyeooqwoU a JO 380 Jomo speqa zeeoaqow pozteacuou oan seng30 eqn23}001 yoy sr, (HTT PE td pow 1A suotrouny a 8 an A pu 754 Jo wosssaxdo 2m Supmnsans ome 4 = oN oh 692 puog s2yor03 fo s2u07 SBuywortos amp ur ways se A pr °IA Jo suonemaWoD aNEaeU, pu panied, Sone) Aa paxome & SLL “RI pezAESOTNON OM SARA FEyNOO|OK oxseo0] Braauoo Ka autoarsno 29 ueo AqnoUP sm aKOKOR yqUYSTESUNSIL ‘2repur feonoptfte|duioo are syUH oxy 94, 22H 2M AO yu eet aNO WON, ‘urmoo se von29f9 a ayts08se 0} 2yssod yu StF 9UNSyRyeRN YOU St SEAGIO ‘89194 9014 pus ‘OW Pe71}22010N pomeo| Jo noun duo mI Jo COTM a SURED ATL yo uoRsBNLOD 4 ven tated peta ust | ff see 20 Sms ron eo 0} en 2 ns a jouopennsong ora Gre CA TO OMA =A same spuoq Hed pazHEao] oxy Buquasep sfeugio FeINOP|OW SAL santa = og caoaiegy Sh = caleg am wow 9 seo pay ds om UL HPAL spu0q pemeoy yet a spuoy some 6 —— (XY ampuong mod fo 0OQL V $8290 4 Textbook of Physical Chemistry Fig. 2145. Correlation Aiagram for localized ‘orbital of Hel Com Is Ie | x Be Be Ht, ocdleed — Nonaslied Mo Mo ‘contin four vans eesrons canbe writen as FO vO Vall FO v2 We FO WO ¥.G) FO VD FO} ange the ove hybridization cannot be regarded as epyscal phenomenon. coordinate system of H,O is given in Fig. 2.14.6. 3 and can be express ‘spin atomic obit, The by the spin molecular rita. Fer example, the total molecular wave function of Bel, Wich ih HOH bond angle equal to 105°. The Theories of Covalent Bond 291 “The proper combinations of bonding and anvibending molecular orbitals of 2H atoms +¥iayy and Y= Yueh) ~Vityd ye ace as 1. From Fig. 2.147, whece the overlapping of I(H) orbitals with 2p £0) obial is show, it may be concluded that the proper combination of two hydrogen atoms ine with 2p, orbital of oxygen is L(H) + Is(Hy). Besides this, group orbital will lo have positive overlap with 2s obitel of ion of three nonocalized moleevlar 8 Yacon Van) 284 Yicy* Vay Vi.n3" Ci¥sv0) + CVapg01* Von Yin) e147) 2, From Fig. 2.14.8, we may conchide thatthe proper combination of two can combine with 2p cand 2p, orbitals of oxygen 3H) trder to have more effective overlapping, we for fist two hyde 3 ut of 2p,0) and 2p,(0) orbital. These ae and ¥E* Vane) Varo s by mixing three atomic obi Vy = Vang +¥ 2p,aug uy wt 30 suo sounes ot Sues Ka posses SL tas! se Ba goo wo sede ej se As suo a a4 200 2 PON aN 9 anuoqea ae sree oyno9]0u TEM oOUIS ‘dz agp Jo au pur zm suoNDI9 30 11 -suoyoxd ono uoistadasaxp 0} 2p "ated 063021 8u® pug peroodr UL ‘anu wy ojoueump 09 1m yno9fou SH, afiguos quando ap ‘(uouphy yor> wo au0 pu ueRGxo WOH fousten pio ae attp cous “OFT UL uF womans 5 sxe TLD, Sayan Soto weep uote ap weap Asura Sj 3098 Mth eyo dad o soy ans Sh A TOHHO ULL 19 Smpuoqni om “9 3A wry ge 20 99 PA HO BL “S YA wen a1qeis ax0ur VA yeuqo OUL “F GA juIpwoqaue 24 II} spo am po (Aes) Sapo sq Ip 20 A pe 4 sRBGIO aD 30710 *E ss) Bupa 2a ju pana om pu (A “Aes) Smpuoquon o seau yng expueg 24 *Kes) Buipuog SSuos 9q INA 9u0 SA paw A “A steyeHO san 21 300 “Z sqyo weBomphy S| UD ages atout aze NaRAXO JO sqrnqie de pur sz om ‘ve Boupy usp aapeSuonzejoes0U S| UBBKKO eau“ 2n Bupoep doy sonny SHO UL ney om Soy, “1912 “BD : xo dz usanyag Sutddosno Jo ysis # se powso} 278 spu0q HO OMT ALL "T 0 anuod nota om Sapnonoy — STERGHO ZENON nay OL pozIeaBy (O81 setts [ego 12910 san29Iour Buspuoquon v $3 Jo suoqeuquuon ay yoo sTeNq.0 ]naoU on NASH a STL “ORE A 4 OFA ya dopono (ove score “6¥U7 Sta wy unoys axe 7A poe YA yo sadeys oUINDS ML £62 puog moponog fo HOH srenqio 28;n2210"1 910410 10 so/810U3 onneion Aapspaoy poostgs fo FOL Y U6294 A Textbook of Physical Chemistry Fig. 21412 Tatra hedral mode of 1,0 Conversion of Loc: and vice versa sp" hybrid state where the four equivalent orbitals point towsrds the corner of regular tetrahedron (Fig, 2.14.12). ‘The two OH bends in water are thus formed by overlapping between the two sp" hybrid orbitals of sxygen and 1s orbitals of hydrogen atoms. For the ion O°. the arrangement of fou love pairs is expected fo be perfectly tetrahedral, but whed two of these orbitals are utiized by two protons, this arrangement is slightly disturbed due ing of econ pir eway fom oxygen. Consequently, the angle of 109°28" between the two orbitals of O* is changed to 105° in water, ‘owing tothe expansion ofthe electron cloud by the two protons. The expansion of electronic cloud means the OH bonds acquie litle more of 2p character. the Fou sp hybid or Yafo) 7 4 ¥b«0)* $ of oxygen are given by the expressions Yep}coy ~ 2 Youor~ 3 Yara Vagos 3 YO 3 Yet) = $90 * § Vino ~ 4 Yates ~ $a nsdn te oti of ele lero om Wg ad vey e ] Ye” Fo) * Chay Va, = Ci, 2.43) @14109) Yim Ci (}¥o00 +2 Vanco F290 +4 Vaptn) * Phy Yams Ci(S¥s40) Wiese “Van 09 + Wags) * Vi) 2413 Corre tion diagram of #,0 Theories of Covalent Bond 295 Wi" Wiske * Vie at 4 Yi te Ye Substituting the expressions of yng 20d Ys, gw We Bet ¥1~ G (Yaga) + ¥29,(0)) + CG Wty) * Yisn)) Ve= Gi Wapgoy+Vap,i0) * Ch Wise) Via)? The fnctions y, and ys ae, infact, the same as described eal and 2.148) provided, we have =; and C, (69 2.14.7 ‘The schematic construction of correlation diagram may be catied out by following. the steps given below. 1, Depiot the relative energies of atomic orbitals of © and H atoms, Since oxygen {is more electronegative than hydrogen, the 2s and 2p orbitals of oxygen are more of oxygen orbitals. The energies of sp? hybrid al but smaller than those of 2p or ion diagram. Since H,0 bas eight Fx) Wg? Vg) Figure 2.14.13 also exhibits the chang ‘when they are converted into noalocalized molecular o Vin Ye T Te »— ve Winnie Logline Nonlin wo. i)(COM COREA) 4 OAIy aA soe Super asemn woxy pout senygro sejo2fou sn0} 24 2oU>qf af am uy p1-z ata, waONS a seNgpO e}NoeFOML swesbe}q ani Se one Jo jrugn 74 eomoUUUkSIR aan YAM auTgRIED Tee 1 feomneumasnue st "54 eqn dnos =, oq Jo gio sz feomounas om Supuogner 2 = = pp Soea pogo 9 Kew opus 1A gn dnl ap aug p09 aus . ats 4 stapuogane venue pam 4 pun A A omy a 0 ae Yh pe“ sro dos 2, Apu vu 2ag009 a vromaamas on ‘gy fgiou rowroamase po Stto “Silo bars ‘SieyGi0 HinosIOH JO BITIEN EET: poets panussne 17 tae u UHoKS ae Heap Oe svorsnpues a 'S'p 12 Bla wong speygI aTMER WeRDsKOD 30 ago KOU Ss Lig a PONg 4 Jo sus 9p wos easn se poe oq fou yrngo on} v yo MEY rromauots coreg A ‘woneuyguioo uv out 01091 ag pow "dz, wm depan0 onsz one “snp pue “ogra 30 steqro 10 now? a,“ . ppaqufeus ur eno siworuyeoo ‘Surpuodsauzoo agp ya. 186 soup v amnsuod ym Sa pue 6 pu Yh pe SA steno roojou omy “Geng st woReRP-« pa = Jo woNeUsep ap aus “pou 29 ser sIqn0 doar? xs Suumoyoy a4 ‘sure UaBAxo on aun Jo sfENGIE dz MIF 29 JO “2 sqeuqp0 Surpaoquou amp se porean oy feu sm pe eos 2 fb sng oN HEA tego own asaxp Jo uN a sUgIO OHNO Jo ‘sri on oy yo se) ar seg (40)8z pur °O)sz 30 saiieus ap aug ceva aoe} spun 9 fu TEES sy JeMDeION aw rj sou a4, sO ou Jo oNFADN) ap prone 9 ann fey po sma outta Gc pes any soe samp 2p TR 2paop woes e| jouw Grvre “ ‘ 4 oop mmtrsmapon ou nvr? Ba aro / aes ‘0 3 ‘PEPE e Sta ar umous ose s paviope 68 sreupsoo> OU “pr'PI'Z Bla) ayRosfou Iau st aprvorp woqze> ou, 3aKxoI0 Nosu¥D 162 puog muoponoy fo souoryy Kaaspucyg porsiyg fo yooael V96E298 4 Textbook of Physical Chemistry Fig. 21445 Contour Aiagramsof molecular orbitals (The approximate representation {involving angular functions for 2p orbitals fs sed) eo 0) NS mio » CYOCYY G36 oon RO) Se 3m) Ko sé Table 2.144 Characteristics of Molocular Orbitas of Carbon Dioxide Molecular orbital Ware Chara Merging nearby lobes Yer No ‘Hecron deny ore co c>0 o>c orc Theories of Covalent Bond 299 factors help deciding the relative orbital energies in carbon dioxide 1. Sioce oxygea is more electronegative than carbon, the ‘be more stable than the comesponding le than 2s ent! 2p(C) =~ 86 x 128 x 10° em), 3. The group orbitals yj, ys, and py ate of bonding nature, Hence, energies will be smaller then those of 2p(0) orbitals, The or to-be more stable than the degenerate orbitals y, and yj, as lateral overlapping is larger than the side-way overlapping igs and y4_ are of antibonding nature. Hence, their als. The orbital y, will be lest 7. The molecular orbital ys being en anibonding rita wil be les sable than the lesser stable constituent octal, Le. 2p(C). The otital 4 is expected ta have larger energy than the orbital yas 2p(C) has much larger energy than tha of 25(C). 8. The molecular between 290) and 29(0) 029, overlapping between 2p (0 ad, tore sabe than the obs andy. 15, The group orbitals yaad ys, wl be more or less nonbonding omits (Cour from carbon and sx from: each oxygen) the electronic configuration of CO, ODPM AWE PH Fy ‘be two o bonds (due toy? and y), two m bonds (due to y and y3) oe pais of elton (4 to v2" and V3)yruq20 Seypuodsan09 axp ve ages 3) "Uogres UEIA oANeoUONDeIe OM 81 Prxo1g woqED Jo S1eUgI0 seInoOION peze907 Aasrmoyg yonstyg fo yoouset ¥_ O0Ea eee camer Theories of Covalent Bond 303 2 _Depiet the sp hybridization of carbon orbitals: The energies of sp hybrid oxtitals wil be greater than that of 2s orbital b ibonding orbitals (the negative combina ‘sro degenerate 2p nonbonding orbits 47; 4. The enerpies of two o bonding orbitals will be salle than those of bonding orbitals. 5. The ener nding oF O¥e, = Yeo Ve, = Ves “The shapes of these xb From Fig. 2.1619, i the two loelized © bonds baweenN and C, and H Figure 2.14.18 also exhibits the change in ener when they are converted into nonlocalized molecular or = GYeye1~ Ci ‘The two bonds between C and N represented by te following combinations ith Cy= Cyand C= Cy. The antibonding ‘The two oxbials ae also degenerate = and Gj = Cj. Thee wil be one onbonding orbital comprising of 2(N) orbital. . 6) Ye Yoo ° ) The tw nonlcalized @ cba canbe obtained by taking ‘postive’ and ‘negative co w Of Yi A ue Thus, we have oi | Se wm — HM —* Fir 21408 Wy, combinations Of Yad Correlation dagram at Fire 0, The caized aoe tf orbitals are simply Coste Nests, writen as We vee coe ©, 20y-Y CO acneo— COCO® OOK JO COO ACCS oO) « (0: ce 00.0 v1 2 Ay unos ae ss myoofou poeoo|vu Jo sue NEES a, () btbsb-bemb+oe- SOE puog mayor0g fo soHomus ) aso posta Jo yooureL ¥ FOE306 A Textbook of Physical Chemistry (iy The energies of ¥, ye and 4 yo Which represet x orbitals, wl be lager (0) The eery of We Wb lage hn yy Sac 2p) ital wil i Fig. 21421 ‘rb ta me ¥ 2) HN molecule © o 248 CORRELATION OF THE ORBITALS FOR BENT AND LINEAR AH, MOLECULES AD, Walsh in 1953 corteated the molecular orbitals for bent and linear AH; molecules and rationalized te following facts regarding the shapes of molecules in the ground stats. Theories of Covalent Bond 307 ‘Table 2.18.4 Types of Orbitals Involved in Bent and Linear AH, Molecules Bent molecules Tinea molecules centred on A 2p,¢A)~26,(A) bial ‘When the bond angle of bent AH, molecule is gradually increased from 90° to 1. The bonding orbital Woe & Prana + is changed to Vise Visayy) + C Vanco + Cua) when bond ungle > 90° and < 180, and finaly to Hue ® Gi when the bond angle the participation of 2s orbital centred on steuctue) in the molecular orbital as the bond angle is increased fi energy decreases as the rcture. Inthe latter, 29 inthe bent structure, 2, ‘The form of molecular of Vane crue ™ CrP)“ Ysa) + Co Hans) remains unchanged in converting bent structure fo the linear stracture. The group of the end atoms of the molecule is antibonding and it lar orbital formed from such group orbit is table when the end atoms are as far apart as posible (ie. im the linear molecel)'. Thus the energy of orbital ys decreases asthe molecule is gradually changed fom bent 0 the linear structure, ‘tween the end som, it is most stable if he end toms are the beat suet)‘9q uro sojnaojour asoq} Uy Fuxpu0g aL, “swOYE Uogre woeMI0q spuOG 2TANOP pur offuis jo WowaBene ajumye ue sSxjoaut opno2jouaqueRHO porenfu0o Y ‘S37NDIION OINVEUO GALVENNOD 91z ead sears Tonosjon oun pow WOOT SHUG THFEAREL 'S1'2 19RL w Wont am sojnsojow Oya PuE TY “aVH JeOUN 30 SORTING, og asp suad2p 9 2soyt sooxayss s02u 210 suowoaqe aouayos Of PUD OL Sumy Sop ‘949 pOUTEDGO STEN “EIVHT 52109} sere spumo ye “02 0-61 Puo -6f 01-9 wolf KprHDU 89] Pue seprEmoW WoMDe} “BI OF “LT wou pu ff 21-91 orf Speysct sasvaiz9p a0 ado 243 Toys) eopuyy2s0 Su0u2e9 9ONPPDA OF UDI 210U JOU Wis s2pnD=OU LL sxioys 31219 SuxpzeBau 90) Seyaoroy om pazeuones use senoaTous Qe PUR AY UO APS JEpuTS V (¢S1-2) ‘ata vent 5 voneandigu0o amp 240 nou ou ‘ogt wen $8] Aiqnapssuo> st ojBue xode am pre JOHNS esa we A@iauo JAK} Seq 60e puog mayoray Jo souo%s sro HE 9700 Pog wis stone G20, ;99]out oop 240) sem, YS1T a 2 = ‘mouuou 9q 01 pasado st 8p 20 yo ores payoxo way au, “sors prox {nap ur sauou 29 01 porsodxe ae sjnaojous HS “HO TAD aly Seay SoHE unas oxy uy eouy 29 01 pao ae sejnsojou "HSH pu “ype ep ‘sqdamExD ry avout 9q 01 potas are suansoj9a0u2pes g 30. '9's Busey sopoaa|RY 9 ‘91 Ghou> unum sey yowya amonas 19 ax} Funpuodsain09 vor yu0o sroanaye umop au 01 mons seam one 01 porodxo 104 ame sovgyea-p Suma seqeonjonr Ay 30j samons a 48 Sone somo} 2m ney sesravouyenquo Butpaoquou sn Jo Riou aey ‘sm, “aroens reds 9 UF TNgH (iz sctosog a1monns 1099 39 UE f 0 ur seosoum engi (y}ez 1 amanns 1w9q uF STH sj: ajo amonns jo stp 9 Supp orsan sua: MB = ‘aumuons emp nog UF peuqpo dst sruquo Faqpaoquou om 9H JO 20 “E Kaspuayg poors%4e Jo yon, ¥ 80E310 A Textbook of Physical Chemistry ined on the basis of sp? hybrid orb a atoms. The sing urwes a 6 bond formed by the overlapping : the two sp hybrid orbital brid carbon orbitals aif the latter is formed by the side-way overlapping of the p, orbitals. oxbitals perpendicular to this plane, we may expect tha part inthe formation of o bonds. Thus, various p, oils andthe ctr (5. and p,) may be teated separately under the LCAO-MO framework." In this section, we focus our attention on the n-clectrons of conjugated or 1 ‘molecules. In the molecu Tot is extended over the entire molecule, These ital may be constructed by the linar combination of earbon 2p 16 where n represents the numberof p, otitals in the molecule. The coefficients in 'Bq, (2.16.1) as usual can be determined by the variation method. The later will + Cll ES) =0 + Gy(Hay~ ES) =0 Cbg = ES) + CyCHa~ B52) +--+ Cy (Hye ESqq) = 0 2.16.2) where Hy f aso = Joa vagdt A (2.16.3¢) (2.16.34 2161. An tylene molecule Theories of Covalent Bond 311 For the nontival roots, we set n Xm secular determinant equal to ze, ic. 4, His ~ Eel Ha Hay ~ ES, =0 2.164) Sq Has ~ ES ~ Hae ~ ES the above de‘erminaat can bo solved forthe vaious energy values. substituted one by one in secular equations (Eqs 2.162) along with condition ofthe molecular orbital give the n coefficients of the 1g molecular orbitals regarding the approximations, the Huckel method has been found to be very us ‘understanding many important features of x bondings. The approxi ‘¢ FH, is assumed tohave the constant value if atoms i and j are bonded directly other Hs are set equal to zero. The term fis elle the resonance integral and is agsin regarded as an adjustable parameter, the above approximations, we describe below the HlUcke! molecular orbital calculations on etylene, butadiene and benzene molecules. ETHYLENE MOLECULE lusrates the ethylene molecule Figure 216. ‘The secular determinant will take the form a-E fp i elno a6)Izp+b+beb opus Supqremod am ude pow gf 9 Bupa o=#'9 svt -¥D o= d's +99 8191-9 (ersr2) 0-99 499 8191-99 ond +908 91-2) ‘ay wouy 'y amansgns 24 3 pda 2 8 om ‘(er 9r2) sa mH ( o=G-m9 +f cers) o=s0+@-2Y9 +90 o=do+a-m9 ‘ae area uosaud aap oF uOTUA ‘suonenbo 2enoas ap u 900 auo saioue axoge ap Suamynsgas Aa paUtNge 9q vo sriuoua anoge a 0} uipuodsauo> sgio ]N9AOU JO U9}24}209 A, ‘a> q>tgolg “oanetou sig ous J e191-0 29 9 8190-9 = 8190+ =" gst +9 =" UA m0} Bxpuodsant> ou, ey ame Kfsa02 30 s19T+ pur gi90+ ‘sI90- ‘2 uonenbe asoge oy Jo soo ey 24, O=T+ ger son Supundes wo waxy pi oa a —m) Sunes vay pur gf hq weupwssiep anoqe ap Jo manoye yea By a-> gf ° o gd oa-n gf 0 0 go og-p g ° o 9 goa soy mn aye ye ruBIMDF see's au, orsra) o= Ele puog maqmeg fo s2u02yy ‘qneajousauorperng omy sor annomow anaiavine core ami (2 =) suansa jo sorftouo 30 wins gp ue ss st Cres (912) squons9[9 ais punos? au, ‘%y, Pargio Suppuoqnee amp emp apnysu0> Ae 9m ‘sonra aameou axeyg pur yiog 2oug segn ZeRoaqouar oy axey 2M ‘Suey 20 sm, (ora) Bey “A 307A (mio sejoojou amp BurzTEMLON fq pour se.9 30 BUTEA 24, (wsro g-o=9 sh Ot) =A 1D gev=g tA + OMA) =A 128 oat ‘suonenbo zjaoos 2 ur soiouo osomp Summynsans G99) g-=-a 9912) g += *g sani yom g “7-0 preoo1- smu, T+ pm 1-=¥ ‘ae uoqenbe axoge ai jo Soar om a o=t-e san Suxpuedeo wo yor rd o=ft y 18 om r= 91(q ~) Sumpos vowp pue gf A weururap axoge 249 30 wWwoRHaFe >Re ZUpHAIA. nooo ape Vv ort a asspuoyy poopsyg fo yoouret VTE314 A Textbook of Physical Chemistry ig. 2463 Schematie graph of four remolecalar orbitals of butadiene we get C= C,=0372 and C= C= 0.602 ‘Thus, the molecular orbitl having energy Eis + 0.602 ,0) - 0372Y ap. ‘These molecular orbitals are represented schematically in Fig. 2.16.3, ‘The numberof nodes press inthe wave functions ¥. Yo Ys and Yate shown in Fig. 2.163. The wave function y; does not contain any node and 8 strongly bonding orbital. The function y; has 2 node between second an carbon atoms. Jt has a partial bonding character as it accumulates chargs between ‘toms | and 2, and 3 and 4 (soled double bonds). The functions Ys and Ye ax antibonding since their energies are greatee then that of an isolated p, otal Ampoxinae —Nunberof ary “ope ‘alee SOO fo | arosiep O92 A & vs b e\8 ee NO oe Q af\ G ae Qe Q 9 WO’) 164 Display enzene molecle Theories of Covalent Bond 315 The butadiene molecule contains four x-electeons and thus its ground state = 2(a+ L618) + 2a 0618p) =4a+44mp 216.16) It we had considered a butadiene molecule to consist of two isolated double bonds, the total energy ofthe system would have been 4ar+ 4. The difference between the above energy and the energy of butediene (Ea. 2.1 04728. This dltference of energy a negative value is ization of r-electrons over the entire BENZENE MOLECULE Figure 2.164 displays the benzene molecule. 4 ‘The secular determinant in the present case is a-E B 0 0 oo 4B (Be cebeeo ic) ee Oem) 0 f a-F B45 0 0 0 fp ae pg {to @t6in o 0 0 fp ewe B [a 0 0 0 Bg aE8 0 synaajou panda nooo suoaso Jo saqumu 2m syuasandat 21) JeA0 poring St voneumns ayy 2:90 fy pu Toy pane el 4 wore uo Sysuap non uv mn 9 sp om wo saoyas 4 aluooqas ayy pu poauotsp mou am sopogou jeee(eo oy md seb om 9005 SALLLNVNO TnSash ANOS Me = (99 +09) ~ (gg +9) G6U912) 8 +09=(g +0) + (ge + D)e = "90 + a, ‘S92 Big wf wnoys ame oh + Weg — Meg 4 Od Lie pug meyer09 fo souoeyy, ‘soinduoo Jody oy yu Kpuataston au0p 99 ves smmraD=I9p eg — OE 4 sonysuog uonsop “Jona saueBop ox uy, “s1HIg10 B]n29}0W usp -ejnoojow Suqpu0q axe oun Supuodsaxio9 fp puro wey J9mo| axe sanyed ABsouD sen 18 UL, de-v= {7 vo(2 +o-{F seals gerne y ‘08 suosandre ABtoua xs 2 ‘2ouDH, TF pus qs te O= {1-2 (P= 9 26+ YO oruna.epanoge omy 3 uorsaudx9 uy 249 sodas o9 ss000ud st poxpour Savoury Ue Aq sip se yats stueUMINa.p jo won ay), xrooot ° oF 7 o ° ° ° 1 rer ore oo1 000 lo ° vel am Sagi a ~) Sopmdn pu Ka w9p ype Sup cassqwoyg ns fo 70318 A Textbook of Physical Chemistry ‘The sum of all the gs equ the total number of electrons inthe system. onoest Wave Exampl pngth of x > x For butadiene, we have 41 = 2G} + 2Ch, = 200372F + 20.602)" = 20.140) + 260.360) = 1.000 a= 2Ch + 2h = 20,002)" + 200372} = 20.360) + 20.140) = L000 lacy, 45 = gy = 1.000 In butadiene cation we have = 2G, + G = 200.372) + 0.602)" = 0.640 4 = 2Ch + Ch, = 260.602)" + (0.3727 = 0.860 ana =a Bond Order “Te Bond oder between atoms rand sis defined as Pa= SnjCyCy ‘The value ofp, reflects the bonding power ofthe bond and is elated to its bon length. One ofthe elation in use is Ry/pm= 151.) = 180 py ‘Examples: For butadiene, we have P extension to Pia = 2 Cin + 2CxCxs = 20.372) (0.602) + 2(0602) (0372) Eilotecules noose ontaining . leteroatoms Pas = 20 AC y + 2C Cy = 0602 (0.602) + (0372) (- 0.0372) = 0487 Thus, the bond C/—C, has more double bond character than C;—C, bon. Consequenty, the Bond length C,—C, is sma than hat of CC In benzene, we find that Problem 2.16 = Pay Pye Pas= Pap Pig = 0667 Free Valence Index where Wis the stm of the bond onder values forall bonds joining atom r, This index has been used as a measure of ease of attack at atom r by free radicals. Examples: ioc butadiene, we have Fy= B= py = 1.732 ~ 0894 = 0.838 Fy= 5 ~pa~ py = 1.732 = 0.894 ~ 0.447 = 0391 thus, che terial atoms are mote reactive than the ce I atoms. t Cycle polyenes F; Theories of Covalent Bond 319 (HOMO) 10 radiation which may ranstion, Thus, for ethylene the lo be correlated withthe longest wavelength of x 1 tnd butadiene we have ME gy, = (a B) (2+ B)= = 28 AB jan = (0- 0618 ) ~ (c+ 0618 f) =~ 1236 8 ‘Thus, going feom ethylene to butadiene, one observes bathochromie shift. In _general, conjugation leads tothe red (bathochcomic) shift. The above expressions provide us one ofthe examples to estimate the value of 7 The general expression of the Hcke! molecular orbital energy levels is available fo linear and cyclic polyenes. These may be used to decive the energies of various molecular orbitals for a molecule and to compute % + x* transition, These ae: —— ah EY Tar paeres Boa 2h) where j= 1, 2, -y and mis the number of atoms in the molecule = a+ pcos where j= 0, 1, £2, . and mis the number of atoms in the molecule order the secular determinant they ae usually represented by the equation y= + hy Poe Bex = kx Boo where hg and Ac ate constant, and are dependent on the heteroatoms, (ohne kel groin a eat H—GH GH) the wave funtion andthe cocresponding energies are given by 1 1 5 ewes Yaw Far Fon? 5 Vee p Bad Fe Venn vino B= 0-186 3) ea Mop ety toga x v J is sot nas EE) Efesooeeore or [Bf (epee ; Beppe aig + tigg on nV woo 1¥ pe [equ smoojouyosardat 59 swtaeeo am 3 dus Taos ®t: 25% 4gtigg atta Dns (Z) Fperor +e Nog a tle T 1 ompes sv (@) 12¢_ prog moqonog fo sauo2yy, — Ev megdl 0rag Ease Lew (Gurpooques) v red am Zp =x pur g= x pun Sie Po BuNBON, uspve9) » sn 288s (2) pom CL = 2-0 0254 Y-19 oratin ys : ‘nny ys am "Zp == * on +, o=9r5419 on 419 ‘am suopenbo 27833524, dyp-o=4 poy O opeoaly ‘0 sovflou Jo sonen 2anp Butpuodsauo> 4 Zh-0 “gz — am uonenbo anoge 2p jo soot sap au O=2¢~ 2 48 BopuMxo wo gory lon “caf go) Zomoe va pm f 6g YaRMANAPanoqe om TWoNDTS He BaP a-» g 0 o-| ¢ a-> ¢ | 0 9 a->l 4 wou empes ye 40) eURELEP FNS SAL) s snug roms fo woanAL V- ORE322A Textbook of Physical Chemistry REVISIONARY PROBLEMS 2.1 Deserbe in bie, the Lewis dese 22 How does the Born-Oppenheimer approximation simplify the quan ‘mechanical weatment ofthe covalent bon? Explain 23 Explan, by sting she trial function of Hy, the difference between molec! obits and valence bond methods, 24 “The mixing between two orbital depends on the f The ditference between the energies of two orbitals, ‘The extent of overlapping between them, “The syrametry of oxi Ihe above factors by evaluating the enerey exp ns and the associated energies of Ht whee y= + R)exp-28)] K=-(1 4B) expl-28) (, R Sas [Le ne am and Ris expeessed i atomic units. Bvaluae the terms E, ~ By atthe flowing luesof R and then draw the potential energy diagram. What do you conclude from the late? R= 19, 150, 1.15, 2.00, 225, 250, 2.75, 3.00, 35, 4.0, 45, 50, 55, 60 and 71 2.9 What co you understand by (i) bonding (i) nonbonding, end sakes gs the statement that the number of molecu LCAOis equal tothe numberof atomic obi 211 Describe qualitatively the MO ad VB weatments of hydcogen molecule, Compare the mets and demerits ofthe above twa mathods ESS eR aie Theories of Covalent Bond 323 pctng the energies of various molecular orbitals ‘homonuclear diatomic molecule when sp inercton is song, What ae the following by using the molecular orbitals of homonuclear diatomic smolecues, ceomrgy of H, is almost double that of HS that of HE, pond O, a paramagnetic in mature ‘The dissociation energy decreases in going from N10 N} whereas it increases in going from 0; 10 O° The dissociation energy of N; is maximum amongst the tiomonuclear diatomic molecules. (vi) The bond length increases in going fom N, going fom O; 1 Of 2.14, Derive the molecular erm symbol 215 (@) diatomic molecules AH. lectronegsive than A (example iE, and (i) Ais more elctonegative than H (example HP, (©) How vil you determin heretialy the IN whereas it decreases inusdy-=a¥ worssadio 2¢9 fq vans} vortsven «2 © 1 99800] 99 store woqne 2 BoABOD auaKyod se 30} MOUS. HZ bo v® po 0 IRM 1=9H ) 1 nomoion mm = @ webu ‘Boymonoy ap Jo KBs wonecTEOOFEp 2H AITO. 1% anotg sudan pm MoH tnoe}ou ry 1029 IE ay) wor poids se pyBus ap You pur Yq 290 punoy st aje=ejou STN ‘few p81 1 2220 2j20e puny pu seauTHON STD 21S2}OH SUL OFZ gamootou paweBnfao0 0 Bwje97H—]—HD aMworow avo ap ST GZ “ye ‘ov annepes, HoH wor snooou ay Jo wennean faIHO sERoOIOM mM eqHDSC BZ “fsouo poog pur antes pug yo santea om and voLO- 160-8 E0~ BOWO- eC HERO- BseEO~ wou ws ase OSiso~ ScrO- OFO~ sus00+ ZsLO+ sammy 67360- See1- BOROT~ 7L0T- GSE60- sanMYCTOT wee we ost wt oats amp Bawone) ‘syoqous™y Jo steng30 ypu Yo pue *D yo sonmo KBoNo feNUaIOd ANNE LZ m0 eo 00 OT sto tO EO sso CD 19K oo ovo WO HO OT ar sco 0 WO ELD OT 2% sro S60 60 980 OT s frase eel ce tae sun sta Ste Puog mu2qon09 fo souryy, sora anor wy possaidxo ep Sumwoy3 ‘9p way Zo suonsuny puogaauop 29305 sans fBibuD RVNOS ap ASIC 92 Jo vowemndijuoo swes-panos# on STUN 62 ao) 0 mip sores ae F299 wu] pg pur Aone wormoossp a Sym HIE FZ Ao 30 se} sors | puOR pu ABsoK9 puog Jo svonemByues awan29 a UAOP AA 22 yowossandi9 9 UNO AAA 12 soy aguDSEC “IN PHP "or spo Fy 2920p ‘SWETGOUd JTASUNOA AUL ‘some (ste aur sofious Supuodsanos ap pus svonoany a4va amp CHO—=HI—H Teoqpes [AI1e 249 20) ey woUs SuOHEUHAORdde ToxODHT aM sqnsojout Spy Jo asmoans ow Bump ar a 5g 2B AAVOCL “OBE 02 06 WOH} asoasuyAqanpas stat poog sways aoojoa ey 3899 9 Jo S904 Teg ur a8oey>atpSunordop wexaep von a A ‘yengvo zejaojou pazs20|aendosde a) _P suopearquoo eaneou, pur sarod, Buren fq pauego aq uFo $5900! f ®2n osqeuqo Surpuoy parnesojucu ag ep MoUs So|A2I0W 70D PU OTH B “wa 30 sjruqno mnooqou paz) yo soossudxo ep Atenenbonas40 17Z ‘amaajowosre 01 papuenca wo suoqzesexpiy pownfuoo Jp pom [90H aMl HOY Aassquays pooptyg fo YOURE YEE326 A Textbook of Physical Chemistry 25. Using te Huckel parametss y= 1 and Keg = N energy for the system C=O and compace it with hat ot Yo— ce a Doel erive the ground ti 2.16 Explain wb: Nand fy re diamagnetic Gis paramagnetic. “The bond energy increases regl om Lip Ny Rhy ed Cy eX eal yoo cnet sling pater {ame 6) CN (NO, oving okies in de ofr oe nth O- Which mote wil ave te peat dsetion eeny: Oo by the(a) addition of an electron, 218 Aran Sp orbitals of Me and ‘configuration. (©) Wiite down the electronic configuration of NH, 223 Draw the molecular otitl diagram cleetonic configuration. Show tat the following fs. lightly unstable with respect to H and H and thas Hy sa ransiet Which is antibonding bowen the two end ators. is stable with respect o () H® + 2H and (i) HY and Hf rangle. {—H" and wiangular ing simple Hlickel approximations with the Theories of Covalent Bond 327 () NH ie bent in both ground and frst elecroncaly excited state 10 molecule is bent in the ground sae. 226 ules, predict he geometries 22 electronic configuration of LCN. 228 Given below are the computed values of J, K, ya, B, ~ By and E_~ Fy a the versus and compare them with ‘R_ Meanwee —_Kharee =a wit (&q.2529 (Bq. 2526) (Eq 2.527) (Bq, 25248) (Eq, 25.240) 10-079 0736 08s (O22 Lots 125-0652 — 0.685 0.794 0977 0.763 Ls -0588 -0558 0725 000s 0573 Ls -054- 0.478 06s = - 00s 0438 20-0473 - 04065, os86 — —p0se 0338 25-0391 0458-0065, ato 30-0330 0349-0059 0.133 35-0285 02s = - 0052 0.089 40-0250 0189-0037 0.035 43-022 0136-0027 0.036 50-0199 006 = 0019 0.024 55-0182 0068-0013, oats 60-0167 0053 - 0.006 0.006 10-0183 ao - 0002 6.003 229 The Njmoleculhas tvcture. Consus the localized and nonocalzed grams, Is it damagnetc ot paramagnetic?euonsanpuow pe penq30 dz ap mo 05s] ue jenqyo sz axnoodsa a moyy uonnguueD sof wos; wonaguue> 338s 9 S98 g30 asap Jo yoea axa ‘sTeH0 (EyD'ds pue (“y's axtonuy 01 pas 29 feu puog 9 stm, Ri0¥9 otuos29[9 Jo uonezmsURU am 0} fans panTOnEE ‘sjenqio Jo Suddepaxo 2on2q 404 ‘sonsUSIUNYS 40 Burddepano fem aps ap 4 paso) Suiddesono oxy Aq pousoy) puog o avo op og aiden Seu, SOT NOM ‘2 vaoa9q puog ojdine yo aauosaud ayy sorexpur stu, suaM20.9 poxedun uP Jo sounsqe a Sune>ppr anaueumps} ajnoqour“N ax, suon2ef@pansdun 22m ‘wore N Jo wonesnliyuoo atone au, tA — OP AYQL0= "A 0 - Ase 0= 9A “Aseso= 8A ose =A ‘wafompdy yoe2 UO LAO Pe UOK30 WO 9H4°9 (0) {quonsonb am Jo (6) wed ut paeoqea sioquin SNO3 TON NADOULIN 1 Fy ofnoour om“ FS punodwos ou 9K “suonD2q9 Jo ue9 OsTP aHOeIOUU OD aly JO pus uoHAxo oy ys nou, eIDU Wo! 190 p Aad a4 pur pa “smooy se 2joofou Bem Jo stegn s]OTOU 1 FeV vonsuen 2qp yur eprrouour Yogre> jo spunodoo woqdiuo> 30 aqui 9] y srrato Jo ois puns ap 205 poqus wey joojou 96 aANICE TET (C09 o waunean oy 30) sxdeyo xno puo mp Yammy 395 3M) ‘voqrs nom 1ovop sed wonoo.sen29 851.00 320) yon redo os pu Ara OVO st MN UO MONS ST WEEE —odD ‘90,0 pao anedou ow se S02) MUM [O=]: se uAMA STOD ANAM AU, OFT samMoa]o =N PuE OD JO STENGIO IeMOd[OWY PazyTEOOT] Aasnuayg poqssyg fo yooqneL ¥ sce330. A Textbook of Physical Chemistry Description of Bonding Correlation Diagram of Nitrogen, CARBON MONOXIDE PF ‘where sp, and sp; are the two hybrid orbitals formed from the 2s and 2p, orbitals of carbon. This hybridization may be ether complete (equal percentage of orbit 2) dependent upon the minimization of el ‘nergy Inthe CO molecule, the presence of two x bonds may be proposed due t> the side-way overlapping of 29,( and 2p,(C) with 2p,(O) orbitals, respectively. Besides these, a third bond may exist due to the overlapping ofthe and the two electrons inthis bond come viewpoint, this bond is known asthe where the lone pairs on C and O respectively. The electrons oa the ‘characteristics whereas those present on the O alom are expected to be directional. For better overlapping, 2¥0) and 2p.(0) may be assumed to involve expected to fo contribution from 2s(0) coordinate bond resulting inthe net 5~ overall charge on carbon and 5+ overall charge on oxygen, ‘The proposed structures of Ny and CO can also be expined from the coelation iagrams involving the localized molecular orbitals. These were proposed by Jaffe and Orchin and are described below. As usual, the energy of valence orbitals of ‘extreme right and left ofthe cortelation diagram (Fig. 18). The 2s and 2p, ori on each atom form partial sp hybridization according othe expressions Weaoig) Bourg AY Yong tiy)= Mays + Woe Theories of Covalent Bond 331 Vy oig)= Yoo) Wary) y= Waa Vap, where 2s the weighing factor! lightly smaller than the respective from 2p,(N) orbitals, the hybeid along the NN axis, Brom these wading and antibonding) wil be is centred on each doubly degenerate and n* molecular obi (bonding) (onding) ble than these hybrid side way overlap, the bonding © The weighing factor would be pats of sand p, but one oxi than p character (0'$ * According to he advanced + The symmety of he molecule reuies that each molec qua contributions from the two atoms.aoe aoa 29 NO 200 5 1g Brpuoqne of sega ow aiewonsp sou 9 Yo ao 29 apo Kop enone ae man on oO}: <9 ue 'D <¥D MAL (6 <2 "Burpa0a) © <* ‘Bupv0q) HOA 4 OAT ath “woqaq vost? suowssaudxo a4) 01 Smproa0e aynoojUs vaSon yo sea agp ts sO seO=fOU je pue at aeIHaP Sqqnop we} I! suo} Om 24 30 Y>eD UO posit2D Nig pue “de 41, 15 -Supuognue) ‘9. <¥ ‘Burpuoa) (Ovi 30 ASzoua n oa 0 soqnanoun approve oq () pee sto. @ ) ee zy MM os! eum yo oe ee ee a oe a he CT a * SEE Puog m2]OA09 fo souOOUT axoqe sfaanoodsat ‘1 (OY p eeuopend so ep wep JON ore oFteg (0% = Oke Oy = OF gy 104 = Ot aang 0 soRou9 UI OURIEIEP UL (ary 1) oman you st ‘wusiep uoneen09 ayy Jo yo] pue Sy sums am we sof osm Jo Bureyd aL, you py es1~= Mg rene OMT How py agi—= ‘ame Q pur 530 ‘yeiaut vonsuen oun yas uopsun0} punoduee-x9}u0 Sgro ou sa0p aqnonjou Ey 24 2 oR} Sp Jo asto0g 81 sosUNPETEGD B moonoanp ayy yo qonur jou yum sagen sz Jo Aqyenuesso ‘suons2f2 Jo smed an, eamisuo> yn CN4§ paw “HA yo yowe my oRDet9 OMI aL, "TENGHO moojou SA pow fA. jo ypea WE suemzo[9 om amo np spUDg ax om pI. 1 suonooj9 om 249 01 anp Plog © 9u0 “pung adn w anny THs a1ADe}OM a, 5A path sy 14 tong 0 Bmpueqnue ai “puEG amp we ages 0 am uo A pe SA STEIGIO eprxouow Aasuoyg pors%yd fo xooqeh VTE334 A Textbook of Physical Chemistry {annibonding, C3 (aatibonding, cy The orbitals (or ys) wil be more sabe than its more table constiuent sol treatment of H! orbital 2p yf), whereas the abil ¥4 (or ¥4 ‘The antiboncing « orbitel antibonding p crbitals y, and ‘The sp3(©) and sp,(0) donot take patito the bond formation and hence wi act as nonbondiag omits Figure A.1b depicts the expected correlation diagram ofthe CO molecule Since the latter has 10 valence electron, its electronic configuration will be wal") ) ig two centres A and tical coordinates define PW wa) vs Ligand ‘The correlation diagram of the CO molecule explains nicely the ability ofthis Characteristics ot molecule to form transition metal complexes trough te carbon ead ofthe molecule Carbon Monoxide The highest occupied molecular of the nonbonding orbital withthe predominant 2p character of the carbon, Tis orbital is mainly concentated onthe side of the earbon remote from the oxygen. This orbital can overlap with a meta groups withthe cent I. This charge on the meal by (08 de lowest unoccupied orbital and 8s back bonding. The sharing oft has the same appearances as ts into a positive overlap, This is tons of spx(C) ofthe CO molecule with ‘the metal atom and the back-bonding inthe antibonding orbital ofthe CO molecule Isuse result into the weakening of the C--O bond. Consequeatly, the force constant of lsvs+l ‘C—O bond decreases which, in turn, results into a decrease in the bond stretching os psan frequency as is evident from infrared spectra of the unbounded and bounded CO. rojecules, ‘The volume element dr in tems of el Ad aa A “The integrals J, Kand Sin the LCAO-MO treatment of Hate: the angle between the plane passing through he fixed plane xz passing Evaluation of Integrals J, K and S in the LCAO-MO aL) (all) (aia) fixed distance can be evaluated (al (ALI) att)aj a yo Burk axwy 90 ‘sued a) orm [rr = [taol uf we * eo fon 28 hg 2| 60 9 te F- am tos0tie + yyegs[E-* SH soe? f Fee 129 am (tty) ba wows 2p Aunmnsns ee ae [efnefaet mf PAD TEA — Hy. 2ft-= (oso x soe (pL THY) "a2 (oA, yAizea-n poe yfig=asr 128 om yA = Ya) = 4 pe ype 4°) rf suowssondxo a wo pie nuowe wy 3 pex8ane aq y Neer) 7 108 am dyes poe (srTEy) ‘baw seafony asoxp Tunmnsqos orm) vg uy) (=zamy) sw possauduo om aay “un anor jo say OY Lee Puog mueyoa0g fo seuooyy verse pene y 5Theories of Covalent Bond 339 ANNEXURE II Conventional Representation of sp? Hybrid Orbitals ‘The four sp? hybrid orbitals yi, Yo, Ys and ys may be represented by four vector, V2, 2, -W v6) respestvely. Figure AI 3/2. whic in each of tockwise by an angle @= 35.27" the anticlockwise rotation by an angle @ = 45° about ‘The coordinates of the shifted point may be obtained ded) lowing transformation expeston Point Q(-1/2V5 .0, 28) x] foosp -sinp O}fcos@ 0 sino Fx Pre Sra nen r= exp olfo 1 0 xe bBo PEt tte. le acre memreeeerl| eevee eres ||| WEG V3 3B 6 372 - lcs ey (2 ty te (2 etal nee eee yee ‘Tis gives WB EV3~° "V3 63°72 14, 1,204 X=xcospcas6-y sing zcos@ sind ze Z Pet,2.1 35° V3V3 6°32 ‘The shifted location is represented bythe point Cof the cube shown in Fig. AIL. Point R(-1/2V3 ,1/v2, ~ v6) tent (2eei| Y= xsing cos0 + y cos zsing sind Z=xsinO+ zcos8 ‘The shifted locaton ofthe point P has the following coortinates I J a= y | Lajia pematene(oee eels x ial8) noe WAV 22 ea 6 2°62 -(2YLY2)-o+0-2 \2 AEM a ye Pt tLe yy / WIVIV3R V2 V2 eG 626 2 r=(S\ aloo! gett Afi eee 2 WEG N36 3 2 (24) “ee shite oetion i ereset by th point Gof the cbe shown in FL z-(S)4)e! Se W288) ‘The shifted point is locted at the comer A of the cube as shown in Fig A xe Pott, La ‘The shifted locations of the points Q, Rand $ are as follows MB RE CRB 6727672eo ap se possaudxa aq ue +2) ba uy wa ywounom aod (PTE Ha) mawoUs sjodp amp jo apmresews ap 01 eopIOdo} ‘pooup s1 sou amp Jo ypBUo] 24), 2]m2>I0u! aq Jo pu> aarsod 01 aanBou twoy uonsenp 2mp sexampu gargs mou we Aq pantosaidas oq ue y] “uonsemp se [ow se apmanew tpoq seq 2 Aiquenb soron est ywamow ofodsp 94 wee 10-4 se pau sy Majeonemempen (cower majonnazET 2) sof om ayy uadt09 4 900 Jp poo 04 G aBim om 203 74 yoqunds amp &q porosardon st rest © £q pagus 29 ue> 2ooqou ® ‘ane auanooye 3059] a 51pUD 2 dp a se wow “ArmueNb tnyo Jo donngunsp UL, oI damn pw pup eaeou an se soaros wore simp Jo vonwzedas sannbow ano2fout a9 ar29) J ou 9p 01 39U nquap afsey> om "21 “gh ons saqnaojou a1moHp ‘ay uo spuadap aynaajout pur suioye Jo suoneanaiyuo> oyuon20j9 amp Burperisiopun sdjay SIM) “sn, aosaud st vonseje paredun yons ou "usreuSeumep ut ery vane panedun uo wep a1ow 30 200 jo aauasaxd 2qp 0} anp st aqn2efout © uy msneUoumem ‘noufeweyp 10 snoufeuesed st eoueisqns ow saynayys Zoywouy sdjay ploy ‘aude © uy aueysqns¥ 30 Spms Nouonaowint sansedorg seuseyy pue peo1qoapyy ¢ nav pegs yb amor regret LY ene ye ZR APY, vt Kaasquoyg yorssya fo yooares ¥ OVE342A Textbook of Physical Chemistry mig 324 Representation of Aipolemoment Component Method of Adding Vectors Dipole Moment of ‘More than Two Charges ‘where Q, is the charge of the ith species and r from any arbitrary distance pont, For examy the vector length ofthis charge of the molecule ig. 3.2.1b, ie, ple 3.2.1 623 322 The given ‘The vector addition showa in Fig. 32.1b canbe convenieally carried out by making tse of the expression Pat ‘where p, and Fig. 32.16, we Pe= (40)r, 005 8+ (-O)r, 008 By Py = (+0)r Sin 6, + (-O P= ((40)r 008 8 + (-0 are the 2- and y-components of the dipole moment. From ‘Thus 7 sin 8 +O) sin )? = Or} + Or} -20%r 7 8 8, cos 207 = Oris rh ary cos 6, + sin 8 sin 8) =O rhs 3 ann, cos(@ - @)) =o dipole moment given by Eq. (3.2.2) may be extended to any charges. Example 3.2.1 illustrates one such case ‘Unit of Dipote Moment For polyatomic molecules, Bq. (3.2.2) may be written as p= fromer G24) were (0) is charge density at a positon defined by the vector rand dr is the volume Ble land Magnetic Properties of Molecules 343 Tor the assembly of charges shown ia Fig. 3.22, evaluate the exp ‘moment. Given: The angle between the ofthe dipole 610" Let us have the origin at 39 charge as shown in Fig. 3.22 Thus, we have P= LAr= GOO) + 2O)r, + (Or, = 20+ Or Now sin 30" Now 464 10° my? + O22 x 10°" my 593 < 10°" san pe Pu 2X10 m5 og Pe” sas xa) gore Since p = (charge) Gistance), we wil have C6S-esu units The STanits The of pis esu em. of pisCm. If one electronic charge is sepacated frown an equal positive charge by a distance of 0.1 am, its dipole moment would be 3 CG6S-<0u unis p= (48 x 10 es) (1.0 x 10 em) = 48 x 10° esu emvee Sa uy waogs se aad potoy> Atanmsod ayy spzenon sp aaneou pur aed pany xmsod pot mp ut pont a "ur ut soesous8 Aqarom) pus sunsoup au yo sajaoqout uy sozusjod sored a uo 0 Kusuop afiey> a, ‘moor se poured st osea109p SLL PIeY. Ro1oopo si Ssearsopsoy>ede> ayy yond wu sense yo souasaud a5 eH ero “a>a neq am ‘SEN a9p Jo SOUT 305 98 URI J8WaHB S12 AONIS ‘seansodsos“unpow pu wnnoea Jo sentanmaod oy ame 3 pue % ary 2 wo J = 2maapp mom g py snesonDeT °9 weo = oswetep mom °g prog ersoncer any om yd paqrered ay eu sup Jo pus 24) aznxousy Jo ap aD 91929 37] (Cory) ba worg sousedeo & oLIovayo auvid TATIVUYd V JO GTALd OUWISOHL9373 3HL NO ORLOITIIO VY 40 1034J3 &) tae EMEN,O fou meu "moog umons se auENyOR Jo uN 249 Sey O9mH/A “UE son H LON wD NW ,O= sy 1g st yun oy, sqm ns2-59.9 ‘ancy 90 19) = sous Spe s2m2207 fo souadosg snuBoW peo oou2yg ero D+ =" ‘mu, ‘uonwaymyod wopentabe w go nope ye soo ND=|2 24, mono TEE. wo ‘ot +7 =D oy sommgeasod ‘ang anoge a jo uns geagadye ue st ajnoofow ap 302 Aamegezod 10 94, 19 9 Buoqe seqodp 1051s, uonezuejod uopeuEHO yeauejod Buipuodsasio9 ay, PI ap Jo puo anpe2au ‘ze (swore) tjond oi ‘smn uy uopeZuB/ed o]wory smog se Shem, marayp 20m ui pazunfd st poy opesonsef ue Jo soussaxd oyu anoatonr a, pty anessansofa ue yo ‘gBvans yun e kg prezoua9 wowour2jodlp p2onpuy ayy 0 Tenbo s9 vonswuep Ke ‘noojout 2x9 Jo Knqenwojod axp se uMOW sf puE “Pea a9 WD a|aDa}aM ® "es yu ssomsea Jo ammseou wt pur AngPvoTBodsd yo nesuO> ay) St aay oro ap" ronpuy oy Terouo8 uy uowour 2qodrp paonp a> sap pu {souosayd am ut ajqeauejod ave uornguisyp eyo amour Suey sjnoojou ry “pansaua# s|wametn2}edip poonpa we smi pi poy 2INa,9 oes © 30 2ouosaid 249 ur pouorsip st aqtaefousB Jo UORNUISP aluanDop9 oA ar seo WI gO X9SECE= 5a TT OH Dg 01x CO9T= a8 1 01 X 2091 = (Hg 01 X OT) Oy 01 X 2091) = sais uonezueiod 40 spuyy quas9p10 qwowon, ‘ejodjg peonpul assruoyg poorssy fo yoognay ¥ re346. A Textbook of Physical Chemistry ‘This arangement of molecules adjacent tothe plates decreases the net ch on the plates. I oy isthe induced charge per unit area on each plate, we wi ‘The term dy 8 known a polarization. The Factor dyg wll also be equal tp induced dipole moment per unit volume ofthe dielectric. This may be undenta as follows. int = Induced positive or negative charge per unit area ofthe plate = Induced dipole moment Making use of Bg, (3.3.4 dielectric as o- ous Ew 2S, 939 Substituting Eq. 3.3.1) in Eq, (3.3.5), we find that © elig)=1 Equation (33.7) the eatve pes 3.4 CLAUSIUS-MOSOTTII EQUATION Dipole interactions Ons N* Poy GA Net charge per unit area on éach plate = 0~ Gg oad fe may write the electrostatic eld Bim the presence of e637) LLeL* be the number of molecules per unit volume ofthe dielectric material and let be the induced dipole moment on each ofthe molecule. Since the polaiation ing presents induced dipole moment per unit volume ofthe dielectric, we have Electrical and Magnetic Properties of Molecules 347 Ie cis the distortion polarizability of the molecule, we have Poa= OE 5.326) Substnting py in Bg, (3.4.1), we get Ou= Na, E 042) 1 molar Volume ofthe dielectric, we will have G43) By, G42), we get So = (4) (a) 044) note] Since «is « molecu permanent dipole moment and (ween neighbouring induced 3.5) modifies to Sa See atl py Sat G45) 5 (G.4.2) in the present case becomes Ging = NPs Ee 646) Substituting Ey from 1g. 4.6) and F from Eq. 33.7) in Eg. B.A), we get or G47 (eleyy-1 (1) yee (1) ca Map) Geleq) #2 * (Beg) * ey lew oc IM Ny g, Gas) (ele) +2 p ” 3e,you 0 165 = 10m 01 IES = esos} 09) (28) 93 Ce) ‘wooed wong tu ab seus dix’ “wins ‘momemadroel 0 + £66001 T= $6601 1.10 {0 Ip 7x MELz poe une 1 Jou gu pp ze = MA sapied 66001 =" (20 o¢.01 x 9 SEE0) £91 ann ag “Gngermod vonssp(P) pur ‘swopertod (Gamguad anpnas20) yoo ouaqap my amsrand ue | puR Y CLZ BVOS 2d “ws'e 3 retered ou tens «pot pros 21 sian Jo x01 ap = d sous SqmsooR sxjoduou 3, suas Snosel ox a 203 qd ou amy ESET 5 aL ouruiaep 9 few anoout ap Jo Pa pum d “xan pte oo was aXe) pat e4_ dN) 98 OK EU Jo AIH pe yea} o KU ny ore sayns2y0y fo sousadong neu OWY pu ji uonenba okaed, ‘Aeidsiq yon pue (16) ‘sha Jo asm BuryeRy wontons atgeq pe umour, vag dt eso West ‘01 soyfpow wonenbo ymosoyy-snisne.y amp ‘sqnofou! sod Jog eso Sn 4% = Py ary om (7¢ ba) sopmgeztetod uonsnouo pue uowtoystp Jo us amp st rgeztefed Teo! SomIS arse) Ba imgeztsfod uoryensaue ap wp whoys axey suonE NoqED parmaC ‘uss oi jo amyezadurey amo youonsodoud AYesi9u4] “wondanp pray aunoaye patdde am ur ajnooqou agp Jo d wowou ‘odip youewaed Jo wavediuoa Jo anyea edei248 mp o}jevonsodoud fqauIG « sso} ony Busmorfos ap vo spuadep Axyigezimod woRWAN ap =H Uy “rss 99 30 aumeiodwor 1 amgeraduoy 1 spuodop urisés snoased yo 43:ou0 Teuzawy 2oulg “uonezuejod uonsiwaU0 2915 agp srommope! a oe sore mn mA] pda eg plethora fq won 2 MOSOFY-TESMEL amp A WOREAE SU aumersdu ‘gym souea (g'¥'¢) “ba wory pautworop sv soynssjou yns so woneztejod 3 apts 30] aq, uononbe rmnosoy-emsmoyy amy se wow, st (S76) Uowenb Noluvnoa 34830 Se aaspucyg oorsyg Jo YOOPEAL YB380 A Textbook of Physical Chemistry Example 3.5.2 Solution Electrical and Magnetic Properties of Molecules 351 Induced poaczaion, Prag = Pay ~ Py = 73.95 cx? ma ~ 5931 on? mot! = 14.64 em? mot (@ Distortion potaiabiity, ONT CO I ak 26.) ACSTR the dipole moment of NB isrepoted tobe 144 D andthe ane ad eee polacization toa about 6.0 cm mol", Caleutate the dielectric content or perm a O€ Nii at 1 atm and 273 K if NH i a per Dvacion oaatn, a= (3) 663) We have p= 144 D = 144 (3:35 6 x 10 Cm ze Pee Pet P= 6.0 cm mol Orientation polarizability, o, = _ B64) Vg 22614 co? mol at 1 atm and 273 K Orientation polarization = % G63) T The sbove method of determining and pis applicable only fr gaseous systems. For condensed systems, the Debye equation cannot be applied as such because of stronger interactions among the closely packed polar molecules. The Debye equation can, however, be applied fa The Debye equation Hd i (cay ¢ ZH) ona nerd )etnens (6.023 «10 moth BBS4 x 10 CENT a x10 Cm 32356 x10" Cm? KNBR) cover a range solution is determined from the expzession perature, molar polarization Py of the (2414 % 10°? mol) = 60 x 10° + 46,29 x 10°)? mot! = 5229 x 10m mot"! Pye Paz! Me 666) S21, 5229x104 mot Dat? pr Hence £121, 5229 210% wot | 442" 22414x 10% mot ~ 900° where Solving for, we et My = 21M, + 2a 667 where x; and x, are amount rections of solvent and solute, respectively. The molar polarization P, of the solution includes contributions from both solute and solvent polarizations. I it be assumed that these polsiztions are directly proportional to the respective amount fractions, we have e 1.007 Nowe, = e/g, therefore = 66> (LOOT) (8.854 x 1 EN mr) =8916 10% EN mw? Pat nPitmP.= (Pit xP, G68)Buoy ow we jojonu ay ‘posearoul sayy st yay suo BuNEWHE Sere a Uvopionsyp ip wey synsor ome ou, “Ure sivaddesypAjoo|diueo uonezumod uot 1D og IX TL gor cc 1 Tw oTK OT TN De DT re) * ‘Arensn ssinoco ofusyo sp yoru 8 Buss Kouobay a, 95831009 2 24) a8n8309 Sdoup uomeztejod ay} pu pt am) “oun wont on @eee ba) (= ie ea tw wy sunac0 won22sIp pray Jo euDAR ay YEH oUeU MON anjer LNLyINbo ee (1 da pring 61 vonezumjod uonewano ayy 30j paunbat st awn ayy © wee ope ay) $8 20024 100 9 00 ZL dos 24) 1/1 sures paoyd uaog ant 4 Jo Sane poe suis 2 mde eon Pe uu 28s RT ra ti 57007 ost For aber 1 900'1 ove sts a1xsoe L001 siz ose. 2108 5300 snoge Aouanbay Jo aaa patzouuoo pomiag soumagns a Sue Aq pouUD.9 S| ZEUS EG UENIS ety woy%g jouoREMMIED FO OL ome 249 z wee (OO) Bae 4 30 senen paaynoyes 9m tay Zuo} wep Goad an sopmoi19'¢ ORL, sicpities “anoojou Fy tn Jo wourou aod ap ere 8 qupeumjon aypoads sy uowenbo afqac 9x2 Aq paqussep 6 sajnoajou pod jo uonEZuHOM Tew AL, 1 ort soe E1001 toot reo sa001 wee seq aisssse ove see ose yammesduua, ty a prmmoat re (3) un 24 paved von ane cep Sumnoyos Lg geen dw won «2 e woe ec « LOY ey . e0X@0_Ubw A me | e ESE seymomOW Jo Fausadouy anauBoy pu pous0.7g Aasquoyg poostyy fo yoounas ¥ z56354 A Textbook of Physical Chemistry Pe P, R Vu Wet Varlaon 4 f ot 3.8 LORENTZ-LORENZ EQUATION, alternating field because of th Polarization further drops clectric field pases through clectromagnetc spectrum to the vi polarization is due to he elect frequencies. The vation of mola, field is displayed in Fig. 3.1 relatively large mass. Consequ mappens When the frequency of the |t-was seen in the previous section cat the molar polarization induces only the eewoieplaization when th ubance unde tay i subjected t alerting electric field of frequency about 10! He, Under these conditions, ma glee field of equeney ditions, Ea, 3.7.1) may GoM _N Pp= SoM Ny G42 p36 am ‘Eauation (3.8.1) cannot be uized as such to ealculate the electronic polarization a the data of relative perminivty are measured by employing alternating curent cof low frequency of the order of 10° Ha. However, this difficulty is removed by employing Maxwell relation ea! G82) ‘were mis the index of refraction ofthe dielectric. Equation (3.8.2) requires that to clave permitivity & and index of refraction m be measured att fequeney In actual practice, the relative permitivity, by electrical method using the alterating current the index such higher frequencies Bq. 8.2) tue even though ‘hese quantities are messored at different frequencies. The reason being thatthe the same tated above, i determined quency < 10° Ez while Blecrrical and Magnetlc Properties of Molecules 355 ch type of molecules and that to the 138.2) does not hold good for polar molecules. ric constant measurement includes all three polarizabilities, vi., the index of refraction includes only exatnples of benzene and water. For benzene ¢,= 227 and n= 1.50: Hence &, =n? (ooapolar) For water ¢,= 80 and n= 133: Hence €,#n® (polar) Thus, electronic polarization of a molecule (polar or nonpolar) may be determined by replacing Eby n? in Bq. (3.8.1), such that mol _N, aap 8a) [Equation (3.8.3) is known as Lorente-Lorenz equation. The quantity ole a2 p is known as molar reaction ands represented bythe symbol Both molar polarization and molar efacton are additive quantities, ie. the molar values ofthese propenies for a molecule can be obtained by adding the appropriate torn values. AB, 1.0 The index of refraction 1.000 516 and its dileceric cons ae the atoms arranged in the mole Since forthe given molecule, we find that D > 1, the molecule AB, its dipole moment is zto). Thus, the arangement ofthe atoms in at 273 K and 760 mmllg is aleulae its dipole moment. () How sonpoar (i.e BHA-B, Calculate the value of molar refraction for CH,BA, given the sane for he following compounds (CHL 195 co mot"; CH,Be 145 en? mot HB 99cm? mo ant CH, 68 ca? ma Also calculate the values of molar etaction of C,H, Br, and Since moar retraction of a moleule can be obtained by the ation of appropriate moar refactions of atoms, we have = Re + 3k + Ry = 195m? = Re + 3Ry+ Roy = 14.5 om? m ® @“appoqyp fezuoq Jo wow jodip 249 SITE oare TET Tao voto T99c 9eewo ersioo reser y6z051 9080 si eioo Lace oo 2051 oreo 00 0000 aaaed pu *ISHOFH’D ono aside sourrsqns rod ainda so Asuep 12 ura My Jo ones a "a 302 DAE) 836 gy (3) 58 (€68) ba om hour om %o ueKp EUS Yoo foo (+5) any ty exp pay ax “(Z'6'¢) Pur (1°6'¢) sb wo] oe 20 2 wooo nmroy na woo wed lop mao reo Co etoetey Sty smb srs ibe 2uano7-2300107 pus 26g JO oun ay 2154. pot Burge kg ‘SNOLLVNDA ZNSYOTZINAYOT 3HL ANY 3AGIq SHL 40 NOINA Use s9ma2q0p4 fo souedoig auouioy po joerg Vee ojdwes 91% 61 punoduo> an ‘soo pepe Homer *\remupssai nny am (ba two “emg ow a Fe = Jur tio (8 €€~ SPL) ="y~ Ye {Tom 9 17 = Tow uo 66 = My r=y ao z= "az 1) ba toy (4) bg BonaeD GAS oun wo 9p = yz +29 ‘bq Sunoxngns uth pus (x) pee (i) sba Somppy 9 9 My + y= My 0 66 = "iy + My = "Oy uopnjos eee odurexy aspuoyg possyd Jo xooan2] V 9SEFlectical and Magnetic Properties of Molecules 359 358A Textbook of Physical Chemistry ical and Magn perties of. Solution Figure 39.2 ilustates the plot of R, versus xy. The vale of Ris found to be First of lhe values of Py a ifeent concentrations were calculated. rom he obi he molar polrzation conto P, of the sole at feet conceal Finally, a plot of P, versus x, is made. The plot was extrapolate if 22-9 Oto obtain he vale of Py, Table 391 ices the dat of ealaaone Table 39.1 Caleutation of P at Ditferent Values of Amount Fraction of Solute 4 ® oo orrrriortsote tae nf ta Aa gem" Bet ‘ea? mol at 3 0.00000 08740029787 78.108 26.620 26.620 ae = ° 0.013 14 0.8806 031086 = 79.196 27.959 26.210 128.54 ar oo1843 08836 oai602 430 2490 26129 17136 oinsot ose 1 032325 80267 mar 25927 12634 lL 392 Theplot of co or am ons yersus x3, — Now Pye= Paint Pie Where Py. and P,,.. ate molae distortion and orientation polarizations at ifinite ition, respectively, Since atomic polarization contribution i ust 5 that 10%, we ave Pare Rew Hence Py 2-= Pya— Ryo 131 cm mol" — 44 em? mot! = 87 em? mot From P, 20 the dipole moment pof the solute is determined as follows = M24) see nao (G5) mn ft the data, we have Fig.39.1 The plotof Prversuss, [foasstecio® ct 2 003 x 1.38 x 10-799 K71N298) 3} ‘Table 392 Calculation of Fi, at Dtfrent Values of ‘Amount Fraction of Solute (87 x 10° mmol Ryden? mot! Raven? mol" Ryemmor! = 6.880 x 10 Cm “G00000 029511 638-37 = 1D, ) nt 2 ae ae \_sett0en (g Barc) 20 Simi te bay eeaurt=av0-aist=@-0id ewomuedye ou, @ 1) Buoye yaa puog Jo womppe 1OF2A 2p ipuodsod ou d= (Hod + G10 = HOM 2ovay ala 8 onDamP 19 ano oNpuod oo a ‘ope stows puog 2 aap oJ soundao jo wouppe sore ag, WotR! “HID J0 mowou pueg mn 01 fenbo 5 wonsaup 9 ain Buoy sauoM puog HD 2am J smouoduco a 50 {ogtppe 20190 puja "(IE “Ha) 1DFHD J0 oawxo we Bye, NOU EHD 3 wwawou aodip ay) wos pug X—D Jo WaaIOW puog stp arena sod amy Bu1eq wor aggre $0802 _ (e828) 9092 _(€/8) 909 _ yoy “asl asi one ‘5A8y am ‘SOUL “CT 81 JOE Jo WMO OMI aU ysOT =9 APH (a9) s00 84 7 = Md 1249 snowAgo S141 ‘ETTE Bg wong “pug H—O Jo mowow puog ay 9q "Pd 7 C1"T 0139 s¥Bue we we pour soto puog om surena09 Fn py 9 'fMO9fou Tem Jo ajdurexo ue Zupye,spuawou pug 2satp Jo voRyppE Jo} 2p St 22230 ep JO os ain qn c 10 51 S9K=pY 4 pny $2 "puEg T}——D Jo ON PUOG a, ota. pe ane og yea ou aco a “sivamou puog jeRpIAmpst Jo Same 3 Alp ot oa Tenprap Jo sone <4) 243 manjp Jo swow oms ain Busoouu09 puog ayy WY Z'¢ UOND9G. UE U9ds Se | ‘yqissod zou 51 1°a192 onda womourajodip ou Zu 52024 SINAWOW GNOB 11's (azrg 11> too [Fg TIAN HON ‘ne 98 OH 20) ‘SL (ore d= sjpaseyp uo} 1090 204 tossaidea 2p Busn Kq paeynae> 29 uso Je}oreYD aor Jo yuNOWE aH, UodAIEg rq 959 200 ovo! 350 J2yNOU StF WN HunsOHBAs ‘q gO" S| OWL aA JO ae once a, ares 2704 a ed 01 oR OA NOM 0} HY AD "ov [9 pur H Aq pares Aono ave suonooye Bapuog am Puy s4p0 Xf UD 219 = 89 gp.01 X FOL OLX SLED © 01 x 09D = ‘on 5] stam pu0g ox ot puog sou puog O=D yoeR amINNS maou aprresp voqre> ut “dues ‘yons sf spuoq 2tp jo mouafuene pu! axp A noW “soqno2}our 2x py (001) mona 01 AAAS Bons Jo NEUEN sual 121 250s pq =P M a - yHowour 2qodrp si 12 pul duno ve Bue. Jo mou! 2jodip 4) was, @ Sci Bog ep jo sary puns stow ajodip Ya sey 22921001 oun sy Bueys oxy ‘012 St anoofout ou wowou ajodrp an aouay pe nou o aau29 a yim SapIouI9 aBxeyo aanysod Jo anwao a PaseyS bo ae suoms0[9

Pog, + (Pocy.~ ex, ~ Pex, )608'70.52") 147D + (147 D~040 D ~ 040 D) (0333) -147D+022D = 1394038 D=176D Pe (Peay ~ Pe) 81082 sin oP =o ‘The dipole moment of CH,Cl, will be pe pi toi + pi = y(-125Dy + 76D +0 =216D Fig. 3118 Orientation oC CHCl, molecule We have Pe®Pou* (Foo, + Pox, Pog.) es (7052") =040 + G x 147 D) (0333) =187D 05) Let the bond moments be resolved into the Catesion y+ and 18 Poe, + Pea.) sin (70:52°) cos 60" Electrical and Magnetic Properties of Molecules 367 ating the dipole moment of benzene derivatives, the study of group moment than the concept of bond moment. For example, in ‘moments, then the observed dipole moment of 1.55 D of ehlorobenzere may be anise fom the CCl Knkage, Thus the group moment of elorne atom the group moment acts away from the benzene ring whereas negative sign implies tha it acs towards the ing. Table 3.12.1 Includes the group moments of a few groups Table. Group Moments of a Few Groups Group NO, CN OH Gl oH GH, NH (Group momen Deiye <398 38 16-158 0 404 4153 ‘The dipole moment of any substituted benzene can be desived from the following ‘expression of Vector addition of group moments. Consider, for exampl. arrangement of two bond moments, and p; inclined at an angle with res ‘each ole. Te aditon ofthese two may be cared out by ang separately the two 2 and y-components of py and py 50 ato give p, and py respectively and then by employing the expression P=@i+ 9)! wwe get the resultant moment ofthe wo moments If 6 and 4, are the respective angles ofp, and p, with axis, we bave PLE Phat Pas PLS A + By 08 0 y+ Pas isin + P30 cos 6 + 008 8) + (py sin + ene, the angle @ between the two vector is 6. Subsiaing + 2p,p,<05 6)!” pau = 4 #4 pp cos OO2 = Sip 1oes sn (@609~ ovr + So EL 509 (GST -)E6E “IC LCST) # LEED = a auaruagosoioye'T wl aeee-='ond pu agst~= "9d smuazioqeamosoye-y 1 pie ECA) coomorion-d 0 + c1Z0 +20 ql 021 50 (0¥0) (851-2 + {00+ (SSI) = ad :ruoMomVORD- 61e'1 = (1060 = L0~T1C0+ 20") = 1+ fOr0)+ 651) = aM -suomormoR-o ‘vat aovo= 84 pm asst-=4 aH smuomorosonyd 4 () axl09 99 (OF) Gs aecy=aovo+acee= WM + sono2s tutod ean ot 29 se suxwou 2pdip om a J BOMIPPE Fee Sydans 4 oan pence aq eur wou =odep xp 2eanfoantd 30 ourowsoy Gey = y(919E + ICO + SoYSD = salts 509 (976) (6° “Ie + 19P0)+ coe) = a? sm ost s1@ aay uemoruned ary S97 LD = a 9081+ 210 + SH¥SD = ql0E1 99 (0¥0) (€6€-X+ {970) + 66¢) = aid sm, eI S@ Bey momo WE (B08 T1Z0 + SH¥SD = 0) (66 e+ Y9r eal 909 Uldr 4 2d 61d) = ud out 09 5 9 aAuY sMoMOWNNKD asvo= 4 pwr qese-='U ara, “0 (a) ond asst=4 aszeaserezei=d ond: ouecuqupoup-d ovo= 4: svamqiousp-au ausr0=a9v0x cewi=d sourusgyqioutp-d o=d = ouaruagonnup-d eee=d + suemmqonp-a aivo=aserxcect=d + avamqonupo souaruogasuped “140 (Q) ney om ‘09g a=" agp 24 arg am Tc1e adam wong vonnjos, sousnjrason-d “4 “0 (4) seuezoaqavonpIped “0 (i) sousrnag goad * sousauoqonmup-d “<0 (9 fPunodo0 Sarwonos oxy Jostoutou qo ap ayoqe9 aanoodsas Set poe : ‘doy 0'a G6 ax auszuaqos0qH0 pur avononouocuDgentE Jo swawoW tod =u, zy Paley “eon en hq pertpou 9 Au sw=won poog yo spre a4, Sones ap Jo wo 3 Ig HOM ABLE =, yp 0 209 29 Seu s] eau yp sone osama a op Em) dott rez = aoui x cet = te any 2 Jo asa at Bu “Ayaaaodsau “q gor ? sea ctmy aman ees Spend oo eve oduexg an me a= A ye 0 dl + whan Casmuoyg yorstya fo yoou2y ¥_ g9e310 A Textbook of Physical Chemistry 3.13 APPLICATIONS OF DIPOLE MOMENTS Shapes of Molecules Geometrical Isomers pSubstituted Benzene Molecules Electrical and Magnetic Properties of Molecules 371 LA-chlorontrobencene ‘The two vectors point inthe opposite dzetions, and hence the magnitude of digo moment is (@ydroquinone) has a dipole moment of 1.64 D. It leads to the conclusion that (C—C1 bonds are coplanar whereas C—OH bonds might not be so MAGNETIC FIELD IN A SUBSTANCE In vacuum the magnede fx density Bis related to the magnetic Geld intensity by the elation p=393D~155D=238D B= toll AL3Ib of Annexure le moment values i in the field of molecu ee heer ne _ fa ene of symmetry ls dipole momes thin a substance Bis, in genera, not given by the above relation, It may roups ae symmez _reater or less than gH and is given by r dipole moment, A few exampl B= (H+ if) ere) the structural application of dipole moment values are now describe. where isthe magnetic moment pr unit volume and is known asthe magnetization. The dipote measu molecules, For exa have zero dipol zero dipole moments. Ths, it may be concluded that 4 molecules with centre of symmetry, and the later are nonlinear molecules. Hence, the structures are ° jn magnetic feld. In SI ‘The magnetization of a substance is directly proportional to the applied field and is ths given by Me xy (Blig where 7 isthe dimensionless quantity known as the magnetic sus Te lowing yp of saan ae finer pening oon magne ee Fi the onder of +108, The magne thus B> H. Diamagnetic substance For sucha substance, the order of 10%. The magnetization of th Bed, negative and has a value of tance is negative and thus planar, Some of AX; (PF; have zero moments. structures are Experimentally, the more useful quantity i the product of magnetic susceptibility ' and mol hme dened os . = (Mar volume) (magnetic suseptiiy) nee Recdebok - (hx 6. Ne Neo « Pp 5 i % Sie has wo wit th oni of is that of oar ole, ma : i 15 MOLECULAR INTERPRETATION OF DIAMAGNETISM AND PARAMAGNETISM x Tag oso Ine previous scion, We have defied pe of magnetic mts based on the sign of intensity of magnetization. ianagnetism and pat this section, we describe the molecular agnetim, se t distinguish between the cis- and trans-forms of a molecule from iamagnetism The diamagnetism in atoms, fons or molecules is due to the orbital motion of pretation of diamagne Dipole moment values have been used to show whether the linkages CX j in p-substituted benzenes are coplanar with the benzene ring oF not. I.4 dichlorobenzene has 2er0 dipole moment whereas 1,4-dihydroxybenzene80 0d 99 61 0g N=N ue io Neo) ss P09 =9 a Db 08 uy SU0N 35 Bear yusapx> aq yun dn 2uy 01 o|qeun are sn pu oytoajow amp Jo vo} nu 2M) Out Pay AfBuoNs are suoNTA2 ot aan fa ‘3ne99q axnaayout 29 6} punoy Stu 9 THIGH ay, “suosI2o|9 jo EUW ousioujg 49 wey 2 wey jeuod st you wonNgHtuo9 SIuo 94) ae spuog pus swory mag suon2ojp postedn jo p su arya ‘sopmandosens onouBeuiid J2}0n S18 eae z wsro ()« =s 3 a9 0 attos 303 sanrrgndaoens onouBearp 1 oq pu awoye yendoxde ayy se won stg au ydooens spoueup ap sn) put osro (1 95a) = "1 ap mp YM Psasgo PN "umpau soawadouog asvasxgo ue w pots Butsoddo we ‘ona 1 prey pond am yo Kouapur aan saquosop "in "se Yeo} vse) ‘quant st suonoef9 Jo suds om (ov onp wwowou ayoudaus oy ‘uonpa pasredun auo wep esto “oyiqeznondeu 50) wow 30d A sp poonpur ogy st ‘as aby 30 snaose ogy 0) osaxd sways Aungndsns snouBeur jo anjen awes 2g) sey aouesqns a “IN, ‘Sion euuoyp 941 auopuedapur s1sua20}2 yo uoRou TeNGIO ay) 2504 ese eusotp a Jo y9puodopu P 3 rengio om aoueisqns {9 40 wowous auBeu jo any ase aK poyesouna djasnu> st wsnoufewrep un 6a wan 91 pu woven 24 popun oun “anouSeurered sy aounsgns at) J] ‘snaurureed xo oneufeumip 517 pue Xoanmadsay‘ssoqus (esr eso souesqns ayy 2 “saouMsqns Jo SUA ya pou oudearrg, PaUeIUBH§ PI Soufeui jeune 2 se Soy se sistsod pyey neuer peonpurt snip ue Wear ONS at 0 2 su “Souestsax oro ax 1 £a:90 mo sip Sep poy peonpur “x Bw aU o:NDOF We JO seD UL SH="f wow one q oat aie sueu Kup yo swowou pouBeur 24), doososon ay uo uomezraueu asnsod ru w sonpoad snip PEP ses! 0 free ‘soueu a}doososors asain wi 0 spus pou anouew uso wy spuBeus Ay ssonpoid sie uno si punoze uonsa Jo Zumwunds om pue woro9j9 ue Jo uopow fo ofp req) 9 anny 28 OTT Pu 6°T SuOR2ag UI ->IR22FOUE 30 Wore Xp 4 sages pauredun jo aauosaid ayy 01 ap sf wspuseuesed jo uowswouayd uy, wispeubewelig ni, “Prey SHeusews paydde amy Jo wonoanp aysoddo oxy ‘peonpoxd 51 Prey eu jewsrxe au Jo wonoanp axsoddo oi ut Sunoe ploy oneusew peonput £Le myno2}op fo smuadong auauBopy reo UDA asta jonsiya fo yoo ¥ LE314 A Textbook of Physical Chemistry Electrical and Magnetic Properties of Molecules 375 The paramagnetic susoe suscepiibility can be worked out and is fou ‘Table 3.17.1 shows the re of unpaired electrons. 1 be expected for 7, at 298 K for various number ar Table 3.171 The lues of Molar Magnetic Susceptibility a 296 K the only ctr which opposes the perfect alignment of dipoles isthe thermal ney Number of Taal electron Spin magnetic Larger the thermal enecny (i. lager temperature, lesser the alignment snpaind spin quan lecrons __rumber S 3.16 TOTAL MOLAR MAGNETIC SUSCEPTIBILITY Oi etal le moe cept ith agra sum of maar ana 2 2 ans air? seen ad cer rng se sum of E9s B.15.1) ant - 5 se joo ei? a ‘ an 4399 12661 x10 fa Wy{ + 22) fe Nal ig + 5 sn 516 16453107 For diamagnetic substances, i, =0 and hence 6 2 578 252.90 x10" Tn = Nn 43, ii’ GOUY BALANCE METHOD TO MEASURE MAGNETIC SUSCEPTIBILITY Thus, diamageetic susceptibility {In the Gouy balance method, the sample whose magnetic suscepaility is required, independent of temperature, For paramagnetic substances, both the c substance, zq 8 usually of the order of| diamagnetic contribution (10 per gram) butions are present, For such a 10 per gram and thus the small werwhelmed. Thus, we may write (3.158) n slom, molecule or ioncan be worked out 15.6) and (3.15.8). Thus, we have Pie MBA Exper. tena set upof the balance method [i 10 = 4x (1.68 » 10° mm? mol eur. ‘The molar megnetic susceptibilly 7, can be determined experimentally Knowing Z the Value of $ can be obtained from Eq, (3.17.1). The value of S ‘us obtained can be interpreted in terms ofthe numberof unpaired electrons by using Eq. @.15.). snd minimam experienced by the sample by consieri segment ofthe sample and then inte(arnt papi aay ‘94, 2oumen Satandsoss wut poowd sem pena 4,01 x I= (aa ,s000 PI susnos) oH) ay ( 8) 2 (3) le) 7 = m7 sm $,u,ONSO=LS0=9.00S=a SWS E = wey oo o0R6=# ON 01 tp= 0 sm 01 =10W Vigan T= A Jorg 01 a00aY = 8 = MY * 50g uo pou ssn gg0 $0 Pe shoe #8 voy seg A005 © u}popuans 2m tsa wT Wo! a > aE 0 ones up fow rp Jo Sseu ward my aFuR 2 aepoqe> ‘UONDD Partin Pye p fan SupApRID SHORES Psedon Mo} SHY -AIED SEY ILD Padova or swourseou jae ny ae 39 won paredun 3 40g wonoa[9 pasdan oe se09 1 ‘granp py apoio ys-s01 eh Sune Jo poss ous UAO ® Jo 4) 92200) 9 Seda Sanbay 20 sonoma “DA-R W a paroye9. 9 we Kgdaoses apse mg BIS, 509) = LUE somonoyy fo somsadoug anouony pwn wounoaig oma seuo9oq (5-81) ‘ba ‘papmppu st uortzon09 Kouesong 24 FT fe wag VE = onnyos: one) cvG zereoduex: on wp vt=m nny 28 “Sm, cn aoe 212 omadsar im ‘ious entered Jo aBunyo Jo aes omy st aadares aq paonauadxa aaj UL, aw foovl |= or] (uononpur S}jauTeur wy Buys) (1usWOU NAUsEYy) ~ = AP. a vn tas o.oo 1 sfueyp 2," muy ayn. 2040 gp Jo AMPA © Ky soBuEYP woDNPLL amo poate 94, 4 ¥ TART “Be 24M amp Jo 2p BUD} aM JO WOU ro vere opduiexe aydures ay Jo aurnjos nun Jed yrowou oN>UE ‘anim rae 29 ‘uanyon yun 29d yusuoMs onouew xp syeasaud yy 2001S apow aq avo puw Aynignidacsns anauSew 2qp or porters} 2axoy stu = asquoyy roorsiyd Jo yoo9nay ¥ OLE8A Textbook of Physical Chemistry ‘hich on sustitting tho data gives 200.4710“ NYG dgx10m (0A Ya $2156 «104 REVISIONARY PROBLEMS. fine the fllowing tems: ‘molecule in the presence of an electostate field. Aistoron and orientation polarizabilities. (Hin: See Annexure I atthe end of the chaper) 3.2 Desice the following: 3 (or stat coulomb) = 1 dyn! cm = 1 g!? em st lenias D=ol 1C = 2.9979 x 10? sat C “The unit of woe ig erg (esu)* or JC 1 erg en ear= 1a V) ent SIN TEV SY a" The unit of dipole moment is eu em o¢ © m 1D = 3338 x10" m ‘The unit of polarizability is em? or C? m NE The unit of a4 is m* (Hine: See Annexure 1a the end of hs chagier) 33 Derive the Clausiue-Mosot equation: led ML 1, gy, (ele)? p ~ 3 0% Explain, why the above equation is applicable for nonpolar molecules and not for polar molecules 34 (a) Debye equation is ain, the nature of plots of Py versus UT for i) nonpolar molecules. Electrical and Magnetic Properties of Molecules 379 (8) Debye equation canbe ued to determine the dipole moment for molecules in gaseous system, whereas it cannot be used 8 sich for molecules in condensed system. Explain, (6) To determine dipole moment of molecules in condensed syste preferable to plot Py I, where Piste molar polarization of ite dilaton. }) The molar polarization of a ynereas that of a nonpolar molecules is independent of te why itis so 3.5 Explin, how the molar polarization vases with the frequency of an electrostatic ‘eld. 3.6 Under what contions, des the Matwel relation D =r? hold good? Explain why for polar maleuls D =n 37 What is molar reaction? Show that is given by y= Hoh M2 Mag, Fa2 pe 38 Desive the relation pC m= 4273 x 10 (Pg ~ Re? mot} (17! 39 Explain, how te dipole momento a azomic molecule determines il er cent ionic chaser 3.10. What do you understand by the tems bond moments and group monet? How oes the dipole moment of diatomic molecule or bond mores determine is percent ionic character? AL Show that the vector ation of wo moment pan ps ince at an angle 0 is given by the relation pie ph+ ph Dep, cos 0 312 The dipole momeat of he faving molecules it 2ro, Wha do you coche about thir geome? 05, C5, HgCl, CH, SF NCO), sie fee on & moving charged pace is known asthe Lorente ven by 008 of magnetic induction 8 is given by basic =10'G (©) Show that cersted = LA minx 10° (Cine: See Avoexae I 4.14 (a) The magetc eld aa distance d produced by alec cunent/Nowing inalog sight wie is (9) ‘Show that Hy the permeability of vacuum, has the nit of NCSp amantzors aout Jo aye an up 3 1460 8S. PE uy s507 5) sem fou MN (Hf jeouou ue 9 gC 9 01 poo 3) Sz Te yds 052 Kappan oso AL, ZTE Or LEAD x (100 9 1622) Ya avers «10m > Hy ZC = CRE L3H LC) A mM) se root t6orT ESOT. ceSHOT 2 wor zr ous 95K sun “ume | ps SiS1 E22 Jom uo ply Zz. = "A saID sO ION JO VONEHTE a $poweee ep! ues odes of 0 SUED Ie a 20} EP Fo Sap woy ng Jo Anygezejod woop a px wom sop 202 Afpagodsa ‘9 8 O1L'0 pur zSE 1 axe 2eKp2 [Ktpayp and Jo Ar}stap parE YoREIyaI JO KPH! ALL rao -1su0—owo Tet ec07 sole BIT wee cz 0.0000 TiO 9S 8800 sc ero te ‘Oy 021 auexayoro% Uw voRnoE 20} emp Buynonoy 2mp wos sHR> YigaIP Jo WawON sTP of MINED OLE (soot ‘yoo ‘a 8800 “ALS sna 230 ‘ywawou sod (9) uone2eI0d node uuso e yo vopez peed OU SL, 6'E 1 9 $251 ‘dno HO HO 1001 dou a 17219 ‘suoRnquoD wR HOU aq 3H BAIS audio ype Jo seu fa 05 Sureco wonKos F Jo wonoexpas yo xopu ip aenaqe moras apt SUSY“ m1 3 ZQL ipo mm TH. 9 8 GEL SOT OHDOT He JO AEP UL, BE bo arp Aago 0} prio} Capel 9 suv] ‘ue puog tp a noqeD aan aS Bz ATrEUCALde ne spuog = PTE "a gy-9 51 pu0q OS WoHe JO HAL NCL I9T SOS 30 Wowous OH aL, $'€ [aze1 ="4 a set = Od ‘suy] ver 89, LOSES HLS ym img ows Veh Live Toe - cae big "mojo powenge ame amgeiodun pew g worrezUIod jou an JO Py (HB) > PCH) () Atlow temperatures Py (HCI) < Fe, HBA) < Py HI) 216 9123369 aa.8 8.9420 89261 8.9027 88825 moment of S0;. Assume ideal behaviour. Given = 88542 «10 CEN (Ans. 191 DT 3.18 The permitivity of gaseous water at 1 atm as «function of temperature are as fllows. TK 343 0014447 ash 520 10700? Nm? 8.9025 8.8954 8.8907 8.8855 8.8810 Estimate the dipole moment of H,0. Assume ideal behaviour Given: 62 BBS42 x PEN (Ans. 196} 3.19 The pemitivity of gaseous Br, at | atm sa function of temperature ae 4s follows ™% M36 3749 024-4308 1027 N'm? 8.9102 8.9031 8.8977 8.8930 Estimate the dipole moment of Br, Assume ideal behav = 88582 x1 CON ar A FEW DEFINITIONS REGARDING THE ELECTROSTATIC FIELD ‘A few definitions in both the units, viz, gaussian (CGS-esu) and SI, needed forthe ‘study ofa substance in an electrostatic field are described below In CGS.esu units, the fore of ataction or repulsion between two electrostatic point charges Q, and Q, placed at a distance r is defined as 20, Fe (AL ae canny ‘where D isthe dieletri constant ofthe medium. For ai or more precisely for 8 vacuum, D= I. If Qy and Oz have the same sign (+ve and 4ve or ~¥e is a positive quanity meaning cat the force between the two charges if Q; and 0; have opposite signs, Fis & negative quan is atracive. In CGS-esu system, Eq. (ALI) is taken as the Lass for defining @ unit of placed ata distance of | cm Thus act or repel each other with a force of! dy (esu)* aya tee om or Leu = 1 dyn!®em=1 (gomsy!em=1 (gens) (AL2) In SI systems the unit of charge isnot taken asthe Fundamental quantity. It isthe ‘unit of cutent that is taken asthe fundamental quantity, In this system, © unit of ‘current isthe ampere whichis defined as that current which when flowing through the two infinitely long parallel wires 1 m apart causes an electromagnetic force of 2 107 N per mete ofits length to act on each wire. Since the electical current is defined asthe rate of flow of charge through a conductor, we have Taglar or dQ=Ide (als) ‘The unit of charge is the coulomb (C) which is defied as the amount of charge when L ampere of curent flows for 1 second. Thus Ic=1Axts (aly)eur) va a - eeaneomres oe eon ee pica nap amnoson ee ww “4 ‘sium om ‘pomewiouney ‘god roy 10 aBsoye> aasod sm » 6g poouauadsa aaiof ay so pouyop 51 nod v 0 wSuaus pra yoous22y9 24140 pat ‘uate fo suai ayy orsjndoa 30 wonaasne yo 2030 8 so0U=tOdx aDURISp EE ooeyd s@rayo sipoue yorym Jo asnea0q site py aunDo te SBaey> Ye pumEsy 2 os penbo st wesuoa apn2ojop oi 81M ww pated nal e'h-eA 1 apm 2 s0H>pf a =! sam 15 woo} sv poreneao aq feu ponewsipey pms opin ind 2yp way ey Gin we oRuryo aegnsod tn» Babu 19 atop woM yorusse 2QE10424 = {fo runour ayy se pauyop 81 san] aA. TenvIDd Teun99p9 =p 230 oF WoqUAADD a= = eet am no-s9.9 Sor 5p ea tp yo sa uD ee suoRSeINUN Bu}quD.p Jo pees] e706 a am 982590 294 arm mnpont wou 29 OY PRG ORO OF (089 401 X 6 662 =) 2.98 OT x 6 1667 = cae aati i Wo oy %P OLX 6 L66Z=D1 39 “Momo 24 eounaye Jo FuuGY UE pouyap 2g WED aouENSGns e Jo sUN JS ut 3/3 pnad ane} ak) 40 UUM nS9-SO9 B YHEISWOD NLDTaNP eH, = Up 01 * 9 L868 > stony 128 om (LTV) “ba UF wd 991 =. poe 50 anes axoge an Funmnsqns AON (ory) 5-9( o ) sun 1S udp ,,01 X 9 L968 = i . ant 2m "aKp 01 = NT 20mg cor) dpe (GF) sam m-s00 N01 9 L868= simp ap won) soup ney a twoug uimnoea us| hq poremdos sory 2-1 on apis: poummen mat) (an nom (STV) ba wong 14 pareodasso8s09 3-1 on spis005 (St 5 gN oO q.Ol X psa's st maumodys wos pou st 'dyam am ‘Soeds (Kndua) 2axy 40g oaeds ai 30 A om anf ss soup 8 G aSsey> tp punore je ypSuans pjoy TeenDeye [oy aL, “pantsod st 313 wou fey pur axpeou st 3 ae ‘49 sprexor simod 1 pur 3 Jo apmarufew oy 0} yeuonundand Anoop st ous cup 4 tp8uay ap !moure ue q powasanda aq ueo pts [etnooTe sp ‘eds uy ‘ay shnamnb sroan v ose 817 prey 9H ‘Se uon st pu nvesuos Ayjevonsodosd ap 51 as048 wert se weno S12] s.quiomar ‘squiojnos uf seBzeND Jo stuoY sw) Gor) a coc mazjoy fo sotindong aneuBOy pun poou921q 2 pueg usomeq diysuoneiog qwoineg pue ‘quoIno9 iis eonog dnysuonejeu asnaoys pooystya fo xoomeaL ¥ YEhat field intensity is the negative gradient of potent Units of Zand V From the expressions geek a (Eq, AL ada ==B er als | we conclude tat CGS-esu units E has the units of dyn (es has the units of (dy (cum) = exg es" Thus I stat V= 1 (erg es =1igems) = 1g! om!? st 1 dyn emesut (gem? yt ‘The following identity forthe units of E may be established. Tunitof £1 dyn eso"! = 1 erg em” eau"! 1 (sat V) om ST units msc in SI system is volt (V). Thus LN m) C1 = 1 (kg ms) (m) (C4) athe mst ct ‘of E may be established. V) SIN my! Vet Var! The Relationship Since between andV we hive Lee de es and let A be the area of eoss-section of each of the difference of V be generated by connecting the par y Let + Q snd ~ Q be the charges generted onthe pats. lectrical and Magnetic Properties of Molecules 381 Thus, cage density on each plate, o = 2 ‘The following facts can be derived for theo apacitor COS-esu units letra field F generated by the charges in between the plats it 4x0 _ Axo pe 20 a “20. Se (ALisa) Potential difference V between the wo plates (ce) ve 2 (2 )\aee0 (ALS ba ~ Da ae Capacitance C ofthe capacitor is ger! 2 (4) cn2. 2. =o(4 (AL 16 Vv Bd ~ Gapibayd ~? ard, Ce In vacuum or free space, we will have aS ial G= sr ‘Bletecal field Potential difference = 2.52.4) a oa ce Be ae el’) catie Comninnsin ran c= (4) «anim rom EAL an (LT, ed -£n£ o-£ 8 cant ‘The unit of eapacitance is fara, Since the capacitance is he charge per unit potential, we have tc * Tig mest 1F = Lag asev) am cry) ba woy 'g Bunmnsqns (@oriy ta) eae e.(P2)(2). — (03) (@)-+ af 9m (SCV) ba woy 'y BonaRsaNS -uoyssaxdxa Suimomoy om £4 wont wnnoes up aoueyep 49 parezeds 2a} Jo sio>npue> 3 1% pu 'y quan uo omy om) “pyoU onoueW pareroosse oi JO asne29q vant oq ue ‘ao sd egy MOYO -9 N 080, zw) $,ON=,9u8y= a wim we ems 1m one pou psn ow wu) ene HO. lone uatsis vopsen0p Pod Pe soso Buoy ap 84 fs, ums 30 agRoUEA aH 5H (corr) wet sav 1s esx a Paps onivos as om nom aU HIND ew) fase T 1p yons ‘P 1 jevorzodd Ayesroaut 68¢ semoqoW Jo souadoug anoUsOHY puD pote par J 07 eooRedaxd Apoonp sty yuouns Burkure> wanes we am 1yTENs v0] 298 8 wos p 2ounsip w pray spouse xp exp pry am ‘siuouuodxo woDg «cw Dt=Lt oem (ew) 9,01 = 0894p 1 = sou. = Up 01 8 HD, OINRS 01 x 6 660) 'MOUOI Se Ie paOM 2q ue, Jo ouoyenbo amp “was ues Uy ew) up Ole NI=a }ONI=LI sug wponed 98mm an uo funoe covoy ayy, ‘puosas td ant | JO Aoojan HO ESO) G30 ploy opeuteu v oy xynoxpuadied Sutmoqy quiojnoa | Jo a8mey> ¥ s9pts00— ‘taansodsoa‘y po g “aBueyp 2arusod & Jo a F Jo suonsanp ayy wosaxdar fp uoyy“uaiskssyeulpuo0a popuetpu eur saxe-> B poe x tp spre yod J98uy oypprux por 2eZuy xepus ‘gran Jf qs poey GE 980120 624 a ys pou 29 ur> g Jo uonvaNp ou, Asap xMy aHoUeL 40 vor2npur onouleu sé umowy st pur Knueab Joiaanw stg pjey neue Ou, ew) 1.881188 ONTELT un a8 (Q6r1¥) bet 09 Ose“) es 8g 30 "UN 2G toy n09 pase 81 a 5 OY Sup 8) = 199 wip T= 91 9104 9m (86FTV) “ba woRy (p) sso 1 @ 4 aun ayy “ssasp ur por poooas od asrasmoo WF (Ha ea *(quoynon wes 0) nso ur possando st "asd ums Up m4 sin 1s mo $@ von stg 2010) 206177 ap “ADR Jo WondonP oop oy seAPUDdied noe g pu onaudeu vyBnonpa Spore I tonow are ye ante” YH EP usury a se unos onsed poking Sutnou wo 200} Houde! >q, 1 2OR9M 20} SPUES gy aAEH nia Uf pue"puddds tod ao TVS yp By 6.8 yg? a ways epson Stay Suour es one Jo str w pouyap st pew opauFew sn SA 9 srmsagwdooun> jnyfummeow Stree Avo ple Asun & stayed apse, “BaanoH “GTY. ba) play feounoere amp 1 snoFOqeNE Mem w a soqod onouseut fe uoomaaq 2010) xn sor tw Suma Sq pouyap oq ue> tod ® 3 Pray fea Jo Ssuoyty a, “vostoda) 30 uotneane Jo 20} saouatiadx9 sues FTE Pend rufous xoxnoue yom oi np rufous x panos poy anousew ® ST ST, ald OUSNOWW ONIGHVOSH SNOLUNISIG M34 ¥ queuing 919013, uue Aq peonpoig lela onouBEy ‘wun ssend pue 82), uaomaq ‘diysuonejoy Pret ‘oneuBey oul Aansyuoye porstye fo Yooene ¥ 886* 300 A Textbook of Physical Chemistry Product of e, and Hy ‘The Magnetic Field Strength AP = dx ONC? SF san Tm At We know that 5 = 8854 107 CNT mw? Hy = sex ONC? S 2 ANY m4) ex 1O7NC? A) me © (29579 10%: where cis the speed of light, ‘The vector Bis commonly referred to as the magnetic flux density. Strictly, however, the magnetic field sength # isa different vector. In vacuum, the two are tl Gaussian system B= Ht calsi ‘The unit of His the oersted (Oe), which has the sume dimensions as ga SI Units Be udt calai ‘where fg is the permeability of the vacuum, The unit of H may be worked out as 4 follows unitof B ‘unit of fig Let a magnetic field strength be Unit of H = ‘units will be equal to B oT Wy 4ex10"TmAT (132) Expression of Orientation Polarizability The potential energy of a molecule having dipole moment p oriented at an angle @ swith an elocal field is given by Ve~peeos 0 Al ‘The numberof molecules oriented within the solid angle" dan (= sin@ 4849) given by Boltzmann distibution is given by a= AerM™ dam AFF sin 9.4049 cant) where Ais ¢ proportional “The contribution of dipole moment inthe diction ofthe elect fed by the tmoeculs within the solid angle davis given by aan = (9 6086) aN = 0030) (Ae7E*) sin 40 dg amt) \d diection i “The total contibuton in the 8 J eP.usin = veh often ‘The average molecular contin i given by pa J Wann 2 srfonoe =m ssf (alls) T By deinen, con a sphere of unit i angle equivalent wo surface area us, This area i (deXsin 6d),~y emus ue uous Teuonetos Tevonesuen Wwasear Pg Mg oy = se araoou op Jo S809 yap ‘yum uo om pu Arenas pean 29 uno axoge pas Sinus a ono ‘aurpqadg-wog 24 0 Bupoay sor} } (-S3} eH _paoxe st ajreojou amp sm, ‘Saxnsedsar‘sanot synoo[ou Jo Sofioud soy poe Jomo omy axe ty pu ty pue poqosqe voretpes jo Souonboyy om sta aN w tg-"y=ay =a wonepes a saoyoy pus 22995 SyBay st ajaoqour ¥ Kg 3 suonepes geuewonso Jo (Nossua 20) vondaose aq YoNEW ap WR suoNEPE —Bujoadg Uo|sS} ‘nauwason2app Jo uorDeron pra sep Sdossonoods renooqouj0 wats ay, pure wondO NoWonaowLN! om Adosso.jvadg zvjnoajoyA| Vv B (Sty) 'bg ‘osm mas @P 9 US = Kp rem Gons g S00 =< pur pyad =x RT Aaaspuoyg porstyg fo YO9rAL ¥ 26394. A Textbook of Physical Chemistry Exclusion of Translational ‘Spectroscopy Order of Energy Difference Diagrammatic Representation of Energy Levels ‘The spproximate difference betneen the two levels of any one of hes ene ‘may be worked out from the following expressions. Fae ( in ‘here mis te translational quantum number and has integral Values 1, 2,3,4, 4 Fa eJuey) he ‘where J is the rotational quantum number The pemtied values of J are 0,1, 2,3, ,..% 1) i Ee ie Ber (e+ ale ‘where isthe vibrational quantum number and possess values of, 1,2,3, _ tite Gren ‘were isthe eleewonie quantum nuriber and has values reason thatthe translational energy is considered i the corresponding translational spectroscopy to be observed is completely excluded, The order of eneagy difference between the two suocessive energy levels for ther ‘motions along with the approximate wavelengths of radiation to be employed for the requized transitions are shown in Table 4,11 ‘Table 4.1.1 Energy Ditferonce between the Two Successive Energy Levels SS —ererevcceeeeie Ener te ation = aE = im molecule fferent Types of ectroscopy nal energy levels, which level. nt enegy separations in aditomie molecule by 1. Each sable electnic lve exhibit Molecular Spectroscopy 395 rotational levels ion) and the energy separation between the two success efinite manner (seictly ue only for 8 ti Eg PT ‘ t E clectzon, and are known at nuclear magnetic resonance spectrum and electon-spin resonance speciram, respectively.‘yp ansod Buouepe9 51 x0q 8 ul aed Jo wats i) 2p aA [ ad se powep yo woHssaideo og) wong ‘om aff taoaiag worssMU 10 vordiosqe (619) ba wero (f-0 14) ba Hoon gap soni peg vondhosge-ue sepa wade ay ‘putes st vorssandxo Suymonoy am poplsoxd u avs G@xoU9 oyFIy 291 01 w a7 KB:BU9 ZOMO| a ‘way yonysues © soene> ajoofouv £q.4 Kousnbas} Jo uowoyd Jo uondiosqe a, 6 soyhonsed © 26 anpéa opsuroemeyD Fey YOK swe uoquiey-i99g ap Ka posaudxa uoyo s ade pinby 20 snooee 1 4 suoweypedso4s-ED9h pur “2s “pare! ‘axeaoINW Jo UORKDOSGE 24, wnBueng 01980" Be “a, mano eur asa HN uotsaudxa 9 nom apf Ausuany estan tt ot ol L oy, an 01 per sig amy “p@ujontin Jo uor¥os v 40 peau s} uondiosge fenIse T we ‘ue aouig “3 wotaxyoo2 uondiosge sejous ay) oy pasar sg WR!Nj00 a ag amy ex / ig dg hon 2s ; fee ome oor 4 van #1 pur 2uprfoo> uondiosqo wosurg w9}oy909 | _ f i ae se nowy sf voneipes jo uondiosqe jo Aungeqox! a Jo uorsaxdxe Teme 241, uondiosqy WIISUE oar arr at pes weit se mary (a) f) swouper snauBewronooye panto 20 paqzosqe Jo Aibaue Jo apurufew Buyseasout amp wy Adoasonsads 30 ‘patsy enoads yos v swdop Zp amu] worPar 16e Adoasonsads soor0N Bog oro wowsuns yo azn a ouoiuodond su pew Seis KeeuORAS (sein uuonoetes pue ‘uoRIsues, 40 Auaedoig out uone}peH 10 uondiosqy au, pads spauiowons9)> puessep apeunws TTY 4 ausnuayo porstyd fo P09NAL V_ 96398 A Textbook of Physical Chemistry Fig.413 Symmetric ‘nd aelsymmetric veave functions of ‘wansions be located athe midpoint ofthe box. A few wavefunction ofthe preset ate shown in Fig, 4.13. The symmetyof te wavefunctions wit tespect an cent ofthe box ae also depicted in Fig. 4:13 These wavefunctions ay laste into the following to categories. Symmetric (or een functions where WO) = YC) Antiymmtric (or odd factions where ¥(3) =~ yl-9) From Fig 4.13, it may be conluded tha the fnctions symmetric fonctions whereas the factions Ys BY fenton. io Wis Ws ae te entisymneic 4 nex yycoo3® Se "aah snk yyren 22 Antigmanstc t (eda) nek ypewwltt ELS gene BE ee ag er ao ‘The dipole moment ofthe system is given by pee ance ofthe electron from the Cente ofthe box. Foran observable Molecular Spectroscopy 399 Vora Ves Voss? Vor Vora Ves | Vou? Vest | Hence, te selection rule fora particle in a box is An = 1, £3, £5, .. Some ofthe allowed transitions ae shown in Fig. 4.13. “Toe coordinate sytem of parle inbox diseased in Seton that shown in Fig 4.1.3 bythe elation act canada Hence, he ile moment opertor ie eoyee(x-! prone(s-$ “The wavefunctions ae given by the expresion = Egy me wey my ‘The expression of transition momen is Since the functions are orthogonal, the integral arising from the U2 term will be ‘zero and thus we may Write Pq a8 in) #2) (in Making use of relations sin sin 9= 3 (cos (8 ¢)~ 008 (0+ 9) sea (n+ my here sn rms have been ignored since m= m and n+ mar integer. fx and m ae oth even nners or both old number, ten nm and n+ m ae. Afzava asaep Jo Komsouaap yo dn Suny a ot snp Ateo4seg St ON 2m eH KuoMs 296 JHA aM pu poy SHoUBEUT x 30 aouasoxd ayn uF dn pout st Asexoua8ep sty “(4Biou9 ours axey ump JO 2%) areovafop SyeuoH sm swuavedoo as3u, “97 qord uy sqwauoduioo ew) 1-a-p-" Farvoqa, pina} ae pu 8809 Is WORDEN aL, Zoqun unrenb oy w |= Jo aFueyp & en ajouip-1090/9 PME Np ‘SL sajonu ove360 suousey a 393 sane Buporfop +9) app 23220009 19 spuEE @ 104 ap oye wes fa ray az woyssandes ay) Mg wows? ae sper xn Bv0.R 9) erep yoo 2 PURE @ oy ‘unstaca rae J todo jo semen pontuad ao oes a= tereg (PJ aery (22) aca ones peznmn wo @ (ares (B= cain ‘IM ued 2M ‘SjeIMOUsJOd oymUIEH Jo AayfeMMouodps0 eM Busse) ata) (BE) artsy (B)]o- ena (Eo (3) 00909 (A fx owow vows Jo uoqssoudes ep ‘SIND HAN ‘2 youueo 307998 wmEDEOW seABUE aT «er A) Bw (4A Ix] A) B 2 yo Bods a (ue = “He jeg soqumu wsnyuenb tds reson aye (umeu wt ppo ae subnet "yoa 91) aqua sew ve pur agus impo POSEN) @ 0§, Po 9} sydumg Zoqumnu wmrgvenb ds oraz anny (qui uy dons say ‘oq uae “2 wane zaquuna seeur pur soquinu aBsey> WRoq BUINEG FIONN & Maeno (2 SF 18g (Gg yoo ( ore asa, “sygeeean ame soquinuwuryuenb us eo a Fmpseos soe eqwannuad9 uo p>FeG SF uojsso1dx9 anoge a ase UD in xD) = Coots Shuto sug som pesado sj cot eto | Shiite nested [ewe a (EC) (oe ae Gr) (ai Wi som Ser ee ee mee aaa eer a “2/1 aqui ween ude aus ap yn sxe uno sn pros mds sojped asa poe inn9 paeypun ue st ‘onnau a searoyis 981ey9 2antsod yun e souze> uowoud y “suosnad pu sUOIONd ame snaponuv Jo sivanmpstoo mew ay "Pj anaUew Yeups9 ap pI" 13M JO said ‘wopoean amp tay sTeap Kiotseg Sdeosamads soueuosas pau o]onu ap ‘yy yo eum 1S ba) xmp = Comyn ty ‘Edoosonsads yan Jo Sade Smouren 2 SSNOSIP MOU 244 “soqrenjou amo Jo ureMOp ay UF AeDAds9“sooofou Jo UOHPONP [ean “Sams 2930} ya2sn £134 301 pun} st woHeIpe anouewon2 30 words foun ujorped 9p Say yoIuse CgpRND Kdoosonaads soumuosey ayouew zeafonu a, 40 po $1 w pu uaso 13] wppIgOF 99 LI AdOOSOULOZdS JONVNOSSH OUANOVHN HVaTONN "4d 0, poo IM 2sou) 20U0q UE SlaquINY UaK top kdoosoueds somoerope a0¥enH950, ptuowney 20} 91M] uoHD9I0s Aanspaayy poostiga fo yooares ¥_ OP402A Textbook of Physical Chemistry Molecular Spectroscopy 403 Magnetic Moment The spinning ofa nucteus is equivalent tothe citculation ofa postive charge fof the Nucleus the axis of spinning. This, in tun, produces tiny magoet placed along ti axis. The magnetic moment ofthe generated magnet canbe calculated with he of Ampere's law iA where {isthe curent circulating inthe coll pee section ofthe energy Potential enegy Vof amicus placed ina magnetic field Bs given bythe elation pleus ine ve~Bu, 429) where ye e-component of the magnetic momentum vector. Let be the angle between the magnetic momentum vector and the z-axis, then He M608 0 210) Substituting Eq. (4.2.6) in Eq, (4.2.10), we get ime, A isthe atea of If ris theadivs ofthe col and vis the ty with which charge is then «2p {= (Number of evolutions per unit time) (Positive charge onthe ee and Aker? Substituting these expressions in Bq (4.2.3), we get ly a few allowed discrete component of angular oc TFT ens @= my 4212) ‘Substituting Bq, (4.2.12) in Bg. (42.11), we get He 8H my Substituting the above relation in Eq, (42.9), we have from Eq, (42.4) that both angular and magnetic momentum vec Ve = Buxem) 2139) Ss enea thats, the potential energy of interaction of nucleus wit extemal magnetic field Experimentally its found th depends onthe value of m Equation (4.2.13a) is usually writen the addition of one more fac ve-y Lem, (42130) 2 where 7= 2rjiyg/h and is known as gyromagnetic (cee Bg. 4218) ‘Three cases may be distinguished. Substituting the expressien of Z from Eq, (4.21) in Bq (4.2.5), we get a meals arm «26 4 (sem } 4 the south po “The basic unit of magnetic momet is defined as repulsion (or desta 2. The potential energy decreases w increase in magnetic field for postive Gr) is vate om Ho orton fy mages i he vou aid ‘the north pole of the tiny magnet is near to the south pole of the external magnetic ‘Te ai wai 8 called he mcr magnon. Ks vale fr he yon Tella ce we Ths lead to mae and more actin ( nacleus is y on the extemal magnet in 6606 10% 9 3 The petal ener rena vchanged fo 20 vale of ‘orientation of tiny magnet is in the perpendicular direction ofthe ext 5047 x10 FT (428) field,‘sopsuen oxy Suro819pun snojonu ay Aq paousudxs play onautea omy Jo sans ‘aq uo spusdap vonisuen w yons qui poreoosse Kousnbayy ay, hi ee wa prmg-Co- 0a) ays = (gta) gig = =a Ca-'@) yg ay soto (177) bal Ka wand se waxy uoosoR US HEAD om How Sona ‘ponuaxp iaiepp spun suoyeed oma yo srmsuoo Bupmys ayy ave So pu 10 31 SPSeysepsaIN | ‘sm, sesersay, aneg on “Ly 0191 aM 1StaV IE (AV) Ge LOL xVST) = 999) 1 LFOSSEES) “amollog¥ $11} WoISEAtOD OM, wa-t- aw avgs7 ay AY uotssande 2xp 6 powyaNe ore soqeos 24 ‘nog prey 3youfeun nmisuoo we uontan; pone op urkze 4 paplons! w909 “reny Jo sun ai ut poviodss ax sys Wooy> avy sa589 a Golf, 7 mods ot) YBMOUL ‘1 0 PIPY & UF BseRODI 89] BJO imp sets Honus st ig 20u8 ‘a eoueriny sg, MS TDN AA Se unos (SuEKMIANAL POE WALTP [apn suoyod £05) ofan Jo ada ates ayo sTeuBls ca a uoawtog Surveds OM, ety Kdossanods sqnoapopt Wonuayo Jo spay 2mp Ayuo sous s wormporas-noy 249 $8 UnOUY 8 ITYS ‘oT Fug ur umoys tnnads oy, ‘taanoodsas“doos8 $45, ‘3 Jo suowod san pur dnosS “49 ap Jo suoroud om “dnox8 HO =x Jo wood ‘uo wwosanday Komp se ¢ +z | one a4 moO) [Ro Sd osxp ZOpIM oR 2y suojand auojfqous a4 0} anp st ann29 3 soyoxd (Sqou aqp 0 anp sf PH puo-to on ye [eusis au, ‘suis vondiosge eam sey 9'2'y “Sey UO st foNDoTe 1h paodee oy, “suovoud [éwjeus 2p Jo aso) ues ime9 doteUOsSs suojad ouofdizou oi ‘snuy, wore waBKxo ayy 1 payoene Spam o asfospy om) ue aust 24930 “Suonord yam pure auoysa o aso) Ue 8 sours 1joud st ‘Kwanbostor) woyetsBk¥O z we pon Japon eq 8 9m 300 waBA se HOFHO"HO sownnwads und peu opouBeu ou4e9 Suysaes jo s3u3e04d Aansnuayg yoorkyg fo yooqeeL VU414 4 Texsbook of Physical Chemistry Reference . ‘Compound in PMR Spectra 5 and t-Scales ‘Values of Hydrogens Molecular Spectroscopy 415 quantity, imensones, is molipied by a factor of 10° to expres it Table 4.2.1. Values of Hydrogens in Some of the Organic Compounds Pts per million (gpm). Thus, we have i a Conpound ‘Flas Buc ~ Ba Sa ~ b= Pet ~ Brow 196 retramethysiline 10 ‘Methyl aleobot i (4299) a 9.78 Methyl protons 6.62 a 977 ‘Dionne oe ‘wb Bact Bagh aes fhe exer eget at hich ean poet ieee sm ‘occur of Protons of the reference compound and that of the given. ‘compound - ‘respectively. 4 883 ‘Water 4g The reference compound is ised i the sme solution 8 te sample oh fe both are under the influence of the stmne extemal magnetic field. The eferna, Re 803 Benzene 273 cormpound which i universally selected for hydrogen resonances in non-aquenn 4 ‘Methyl eyanide ail Chloroform 23 solvents i terametysilae (CH), Si on TMS in short. thas the flowing a 7 chara ‘Acetley. Mati protons 18S Nephhene an * Miva singe intense peak since alth twelve drogen nue are equivalent Alice pots 028 ———“Saphuscac 16 * The hydrogen mule in TMS are highly shielded as compared to thos in the Fsomment “The PMR sgl of ez=e protons appara lover ld (7=2.73) ax compre to rani compounds ané hence exhibit resonance ata very high-field stength of rotons. This is atbted wo the circulating curentin benzene due (4.409 2T for 60 Miz radiation) wich can esly be recogaized, those of aliphatic * It has Tow boiling point (27°C) and hence ean be readily removed after the spectrum has been recorded, In view ofthe limited solubility of TMS in water, the salt (CH,),SiCD,CD,CO;is ‘commonly used inthe solvent, ‘Two scales are commonly employed to represent the vatous signals. These are: () the 8-scale, and (i) the ¢-seale. On the 6sale, Sis set equal to zero at the reference Deak of TMS and it increases dowafield. The only disadvantage of this scale is that a larger value of Simplies a low-field resonance and hence a low shielding of the aucleus with respect to the extemal magnetic field, Tis disadvantage is removed in the t-seale where TMS signal downfield. Thus, a low value of me higher value means the nuceu each other by the expression 1210-8 Fig. 427 Ringeurrent de tothe ciecaation of electrons Problem 4.2.1 For most organic compounds, the +-v characteristic of the chemical environ to detect the type of proto that is pres Feeonds some ofthe t-values of proto Ci)—Ch L New cH) cH ™ wo om 5 (©) Mach each of he components with the eoresponing peak (sy, or example, the peak 7 represents the compound VD, hetnical environment: * Alternatively, in eras of frequency, we have 6: ae — x 10° * Fted feguoney of the pcecy Breen u@eun yuan ap iv Bow fopoanod ut MOREE BL WOK ou fa 30 pow o ss oy ‘Sjontwodsox “wosaxdos g poem saduosqns amp oI04 ing 4 meg) BN = Bq pu ha (obeg Pg 2 Mf == 4 snopes ap &q wan aq nou 44 y woroud 30 Afsou9Tenuerod a, ; vices : || -y woyond 99 to q woread an Kg poesons8 pra mp st ng + Hy 2 acew sey oma ay ves pay me SUL (By BED oN one rx ay jo mag 5 conDeap urs 99 CF SE HoH ¥ Wve 24 TMouteeetonam yds my g vonnt ap wy, eid my HD, vy woroad sip vo g wovoad omy 5g rm een sry wowad axp &q potsosgo pry yenmne mp SOLS naueur yeuaya atp jo uopaanp aysoddo ayy WE HOTA V LO fe saiear 1 voy “unde-0 seq quovoxd op uA wnd5~D soy sng m1 BuLH0} ‘eq wood atp yo uns a1p vod SUL 1 Yoox! sao amp Jo poowNogKIoU ‘mp sopystog uso 244 "BEA BOI PI tds aga ane ued uojoud Y “SuORDENAIE yofonu aanoe o1eufeut Sunol orpunonns ayn uo Bupeadep sapysoq "uorerd w kq pa199q0 ples ‘SNOMOVHBINI NidS-NldS AHL seen por-g 2 (001) 3020645 ¥ 2501 TPE K = “wormperJ noo grep ones 2205 Sone ees any Bota Saves yum 2 uur JO Cones AU, iy Kdossoupods 207201 ovr oFs= ote «9 itso set Set= 0591 we s07= 0821 1st et = one ome fe cela 7 A wm A HD} < fptHOw< pau omg we EE L= on0Hr ste uz ot sa ® 0 a ° s 1 feed arom Jo uomemdos an 9 prvom ey “s2725-2 pow -9 “HD SHES aap ‘nyo yowo Ut oun SHE, 0 25usapa Gu UT] Gee Jo VoNEIEGSE 9 ssaNds (2) m ow smojeg se 51 sypod jo joundisse ayy “sm, SOREN ETL sans, swoeoy sarranpKD, SWL amon ‘moteg poqUosep aye seas pur -g "7H Jo sua any Sp, 01 2araFr pM Bu GoRD JO UopeEdes au, (2) PG poomot am spreso) eed auesoyopes> a9 wos See (eH 98 ~ AK Orb =) HL HSE SL ead OJON? ‘uexayopSi9 Jo 1p PUR ZH OF WES! Head WO}OIOTI (a) Led amoaton Gno'ny < Conta} <(o'x'a)2 < Cfo < (SAD opie Suumopos a solos 0 pasadx9 ase sojnoqou UAAE-u) suorexd s409 Buipps ay, ‘vondosqe 2u0 suo 1gHNS Hus 25004 Pu TPONUAPE uognjos ‘Rad aurxayo9 a1 01 2908.81 "a AW o9 ead wHOJIORD ap JO CEH HONHFO 2AM 29 PION HAL (@) Kaspuayg rwowtyg 0 YOURLY SIFA184 Textbook of Physical Chemistry Fig. 429 Vartation of potential energy ofa proton inthe presence and absence of neighbouring proton. ‘The levels ct and BB ace destabilized and those of and Pare stabilized PMR Spectrum Effect of More Than ‘One Neighbouring Proton cs system isidiated wit then itcan be concluded f to occur in the absence of radiation of 60 MHz (or of any other frequency), 4.29 tha the single sbsorption pi interaction (shown by broke ‘to symmetrically placed adsorpions, one with c-spin ofthe ne and the other spin of the neighbouring proton (shown by absorption comesponding tothe a-spin of the neighbouring the high-end field whereas that ofthe B-spin towards the low-end under these to peaks wi absence spin coupling. The spin-spin splitting separa ases very rapidly asthe distance between the action is transmitted through the bonds. Tn ween the next nearest neighbours. Moreover, the splitting of A occurs due tothe interaction hbouring proton B, then thete will also occur the spliting ofthe signal ‘an intramolecular behaviour, ie. the PMR signals of one miolecule wil fected by the protons of the other molecule. The spin-spin spliting ‘separation between the component lines is also found to be independent of the external magnetic field, In organic molecules, the spin-spin interaction may involve more than one ‘neighbouring proton, Take, for example, the methyl aleobol in which the hydroxyl proton interacts withthe thre identical protons of methyl group. We consider now the scheme fo this type of interactions. We restrict overslves to the simple type ghouring prota dos not change. This anions, in fact the selection rule for th miler sp Molecular Spectroscopy 419 ‘of molecules in which the chemical shift between the involved protons is much larger than the coupling constant (the separation between the (WO 5 the same signal). Such types of molecules are abbreviated a5 A,X, where A and X represent the two different neighbouring protons ina molecule. We discuss below the scheme of spin-spin iteracoas with the typical examples of methyl aleokol ‘and ethyl alcohol ‘The tree hydrogen stoms of methyl group bave the same chemical environment and thus have the same shielding constant. Consequently, the chemical shifts of and chemically equivalent nuclei do not affect the spectrum and can be ignored ‘Thus in methyl aleabol, we need not consider the couplings amongst the protons ‘of methyl group and should consider only the coupling of methyl protons withthe hydroxy! proton and vie versa (See Annexture atthe end of the chap ate considered below: Coupling of methyl protons with the hydroxy! proton The methyl protons will ‘observe two possible arrangements of the hydroxyl proton, viz. cand B, and hence the field observed by methyl protons is modified in two different ways. Remembering thatthe field generated by a-spin acts inthe opposite direction and that generated methyl protons Bapiet and the other to the field Bye + Buscn)= These are shown in Fig. 4210, Coupling of hydroxyl proton with methyl protons The hydroxyl proton couples With the neighbouring three methyl protons. Each proton can have either spin or Bespin. The total number of possible arrangements which the hydroxyl proton observes when each proton of methyl group has ether spin or B-spin areas follows Proton 1 Proton 2 /\ fax 88 aja cop ou -Thete are eight arrangements inal. These fall into the following categories: 1. All the thee protons have spins 2 Two of them have c-spin andthe third has B-spin. 3. Two of them have B-spins and the third has o-spin 4 Al the three protons have B.-spins.wos Soya 2 eka powsep ap 70 Y>L Pu an ov sarogjoo ap Snppe Aq poumep a ues Saou TeUHPPE UF NADI ap a8 ugnona sae uc sans am auMMEEp 1 Kem KE OY uwnnsods YAN © Surpiooas e:ou08 uy jonuoyo om soBueyo Apo spjoy anoueU woxoyRP we uNEIeAs Tearce2tp o puadep op syrys Teoma ‘put, sao 9 UO, reason 5 we patjeat oq ue 20u0 A popu. 2yuryaour uanguenb ai £9 pasSee 2 s249W04 "UE YpIYN ‘paungo axe supe 1pm 1d ponjonuy 2p woamiog ys jeomuogs 2p ays s2[no2f0u Cy 430 29w9 Ur quo aeons 09 a ssuSS agoge a 6 Woy S908 wa aiDN iu whi So ‘yeoneuBeu)useatnba u Zuumoqysicu am sn paydnoo sy vow vj Te9098 Uy poo dns yo es 2 of sna sft Repoisaun ao mapa wn! HA eam} a pun texan Ang (20 29009 fats) Sudoo n-ne Jo coven a foe woe oats Suprodsoos por omy = Tom oe pt Jeo 0g Jo aout wn) 2801 fr yon 2 voroid [Cxoxpiy yo asom) seatoys wonduosqe ov 241 ‘0121 wondiosge anoy pur suo 19 an HN 09 JO WOU HIPE © KL suotoud (Sqout vexop Aq jondosge Ter Kdossouseds sopo2qoy OF Sty ur unoys are osauy,suotoxd yhipam Jo stusmaBueae Ep ano} 241 J0 Ye 7 Buupuodsou09 sav oq) > (mG) -wojaq uaa s9pz0 amp worfos 1% vowoxd 1Axaupy 2p £q paxiosgo 1g aye apayauo Kew 2x ‘Py aHaUTeU use at se Uorsenp Sues 2m ‘stands 6g paysouad yep pue Uonorrpausoddo amp wr prey ayy sorezouad uds-0 ‘am Be Fuuaquiouoy uooxd AxoxpKy ap Uo prog an=UReW aM 2 Te ‘suas asa o Yoeg "ouloBvex de 107 Joye Suosgo asx We 187 sun aan 2q rt suonad jfqgou Jo wowatuene 21 pu gz 30 ft pu OZ HD Sm2oqo suonosd xoupay Jo soqumy oy wip suRaKt 1 “Aoanoedsay “| “E ‘EL 18 sauoaqe9 snoj ax0ge 2qp Jo YoeD Uy sUoHEIqUIOD YoNs Jo sequIMN =H, rove Higau o wana eds VoRMOSDIAB OFT BM Ausruoyg poowed fo wOURRL Y OthMolecular Spectroscopy 423 General Remarks about Spin-Spin Coupling High-Resolution Spectrum of Ethyl Alcohol Ethyl Alcohol ‘Spectrum in the Presence of Trace of Acid or Alkali ‘The PMR spectrum of dimehylformamide at 40 ME and at room emgeature i shown inthe folowing figure \ weamy, ‘Sumoqoy a9 ur nous se ext JOO] pIMOM enDads YAN YoRNJoFaL-mo| JM) “SHG, i j fugtHQvo'HD @ SaptApo HD ® ‘am spud waa my tu suojerd yo stan Suapars Jo apo poroda mL, 2.0adg Yd MoUMOSRY ACT © t nd SHOAHDOD"HD ‘envads upd wonnyesat yy puro mo} sr JO sseq si v0 spanoduoo om Soynoney an YsMEuRIP oF aHSOd St ONoUYH DTPA p puna yor pavadxa st (puedo Jo syed puooes way Sypoodsauos ap oy 385 29 ob ano weg IS ENON IM, ‘wor unoqys avo 249 01 payee uovord » uasandax sane agp 2] Sune SuAON 099 3 ‘rpaypene vovesd » suasaxdax sous 4) 2ous“() punodueo Jo rad sn 2 JO Te ‘vey sy yom 9 or papas ()punodioo yo yead a mp yo ama a,“ ‘ud Sonmonoy a9 way pagsfungp oq ew 4am examoH “(I pam) sum ‘eoads wonnjosar ot [eomuapt a $1 wondoox> Apo ayy, "apes wonnysos no] Jo siseq 2g) wo efqenuapr ase aeImauoy femionas ak YIM papn|n09 29 —# = DAHA (ad sword ea0p1 "pot00'HD ry sep Kdossouiads somo 0H f vsraxop proton por (uon wad ep00205) DFHQDHO'HD o jo van ame 28 por so] AN nN BooTE DRA‘ Jo ae sMDNUS LL Uuonnjog ‘son Bods oxy 20 adnan ess uot oan 249 andeoo m9 UL 5m goq aousy pr a] L194 so100000| [NO Pino wonton pa S19 29 027) dneu8 Og 29 0 seou dos? you ann sy ead pray a] se dno 77930 voto aw o1 np SY Wed. mays uds-ndsseaya pry mnufeu pu afi mo} wd sep Boot ou Ye apoutew Zutueyo eu peoeyd 9 m9 29 vo paysndupsp aq weo Surg ds 391 SOPH'D equ} ojnoqou Suey op|maDNy TEmona =ygES HE WAP THA ezpwordod [ead of « amt poduegoun "sseq orm 9 vo St 25015 papnjoxe 04 Aru [NO pamoseuonme pransal ep Jo asn90q mp a 01 INP 2AEW.D PHE HAGPOP AML, () ognjos asrusye ropiya fo yooaneL Y yey426A Textbook of Physical Chemistry Problem 42.5 Solution eave are @ © Since the two spectra are ot identical the two compounds are distinguishable From thee rion PMR Specra Peak ?ia both the low-resolution specra wil split four a the methylene group is tached tothe methyl group Sirllaly, peak 3 in bot Given in figure isthe low-resolution PMR spectrum of CHO, Suggest its structure. relive aren 2 Analysis ofthe spectrum (The relative areas of different peaks suggest the presence of two methyle (peaks 1 and 2) and two methyl groups (peaks 3 and 4), (Gi) _If we subtract two methylene and two methyl groups from CzH,,0;, we get iO. The later may represent two CO groups. Molecular Spectroscopy 427 “The probable strueture consistent withthe above fat éx,cocH,codn,cH, Given in figure isthe low-resolution spectrum of CHO. Suggest its structure Analysis ofthe spectrum “The relative areas of different groups suggest that cs nocd, an y ° ‘Given figure isthe PMR spectrum of CyH,O,. Suggest its struct, relive ne, alysis ofthe spectrum ‘The hydrogen stoms represen by the peak soup. tached to a methylenesm poy am “ON “dn08 Je Buy 39 Fn a ‘9N0-oNEWHE Ue St PunodNED 2p 29S °S yowzouuuks posed ae yom sénos8 ya yep oa oso {poe 7 sad wa spayouo> Kew ax “uoneaLosE SAA aay “sfonRoadsos “9 PUR "p30 289 pur So's "361 =2 1 syd st fq paasudassuorosd jo soqumuam ‘Sm, NoFHO"HOOH 98 anoge 2 tps teHUOD amIoNAS ALO SLL, pouszuog #8 ‘np suonond 2 pue 2 “1 yo aoussnd op saroxpa 2 jeu au, “¢ -dnont pane suow uaBoxpty ayy yosandar sm pu z S800 UL,“ psy » 99 ou Enos sry, "ws8euphy ane we FuIVOD Anos w yeasadas Aru 1 ‘Gc 30 souasaid ap vy simaddeyp 1 eed 2 oyna vou aye yeod sup Supuasandan suovoud amp et “peoje ain ud yo Jo souasal yp 6820s B07 ua SO ow BOGE, ino phew © oy pogpene oe od sp Bupuosexlor do auayfqoun ¥en pagpene ae ead ond up weap isons |Z | SOMBWOWU anveya WM ZO'g = 3 sumupsade a fo ssGouy uonnios “panesineo a9 Jo amon aygeqoud

oUu 24, "ANd J0 25019 Un asuaTH 220uN 39 OF ypOdx IE seus ysa 2tpnuonbasuop “AV yo anea 18s a4 3 2509 s]249] YPN OMT OHA oomroq aou2xayr uonendod ax wey Ja 29 259150 430 20uBFa}9 au, Tava] Jedd xp we parejndod som 5 ox3] wen (aay st mew USIP wewrzyog fn Ka pousanod se syonay om axp 2940 suons9|9 Jo vOANAENSP aAme|a2 UL, 401 X €) wnnseds onauBemon29p9 2p Jo uo Kouanbayorpe 3p uy 1X 858 = LEO Ga 5 gl x 980) =4 s souasapp A@sau ox ssn 999 ¢ See —ssned resnonp aj ® jo 29p20 stPRy ‘oueus uaa ye wonooy> Jo sfona} om) HY uoDMIDy ARJoUD UF SOURI2Ip OL, eh Koosousadg somoetoyt pou anondeuyeusn> eo cea eh uaspop we Jo aus ree wonees ou Cer aid -wonoeme ou ¥ 01 ap 2480158 0s uonoanpayusnony ey feu ku pores mn ands uy paseasour pou onoutes fone a wots oud ‘ue vow Sune smn ue eur p30 fod pe a 0 seo tue Supp 30 pod you 21 uonquaun agemoseyan we sy ue paressu08 am) ‘yin uy onze Jo Sons Jo os se paoUse He PORN Au Jo rots onoanp am 6 9 suoneues oy, poy anouBeu uaa oF oNOUBEW UR seranu ain oetanap dejo ray sey Spey smear mn jo Glove kBJOU ONUaIOd SAL Ey Big anos am pjy apeuFeu qe M4 pueda jo suonENeA au Jo uoneuen Ewen wi-stw tg 8 e)-= wen w=" om 9 s00(14 9p 8-) g—=4 188 an (©E) ‘ba oy jo uopsaxteo an Sunransgng (sew) (9 900 "“t)q-="a-=A voyssaudxo ann 4 ond stg pray onauew x ur paoeyd ways uos2oj9 we Jo A ABI0UD emUeIO’ ea Preig onauBeyy oufeutjouoneua}20 aL Tey ha BUey fy ui umoys se umpuowous syndue 249 JO 7eH) 07 280% StauBeu an Jo wonoasp a i seat (ee) bg484A Teubook of Physical Chemistry Fig.434 ESR signal and its derivative Hyperfine Structures Molecular Spectroscopy 435 the signals are ecnde sth derivative of the abortion cave wih eet the magnetic field, The typeof derivative which one gets is sown ia hg at Nem B-(Ue y ‘The interaction of the magnetic moment of an electron with those of depends on the lave decon ofthe negnee moment he clesion lee, ‘otha ofthe proton. This interaction eng) exese! ss amgm hae ene now sthe hyperfine conning eosont othe pene png fepreseats the exten of interaction between the slecfon sad he 4 imercig nutes The separation between these two absoepions isa. Thus, th constant a represents ‘The electronic energy including the above iteration energy becomes V= giigm.B+ am, Thus, for a given value m, the potential energy also depends on the valve of my, Fora proton, we h andy SE em moi bv Bin my HD Bhhy Zale : iy ya - Yanan =~ U2) EHy8 and Beem m1 Ble Tele Where the fist subscript represents the value of m, and the second tat of mp. The variations ofthese potential energies withthe external magnetic field are shown in Fig. 4.35, The broken lines represent energies i the absence of interactions. The value of B at which adsorptions are expected (only schetiatic) are shown atthe ofthe figure. For example, the ESR spectrum ofthe hydrogen atom produced by electc discharge is shows two ESR frstderivative signals with eparatio ‘The energy of an unpaired electron coupled with two nuctei is given by Y= guigm,B + amy * cam)pew ON ypuosouo ay se asuanut Se 2 2 fs 9UH BOP, See | Sid possnosip a= 1 wonoesany 3t9 01 sp paasosgo xe Safonm agp ys UoHDesUN 9g UO 20 ‘pansosqo 9q {1M S90! soseoqns oait\i4 ui-= Hw wits 4 . (ey Fup Aeanoedsa Fe ; a pu Nw 30 Pay PLE puodosoxp pu “uo anjea amp swaeanda Eo ng am aI0H 4 wins tw 4 tu ie wits the eB - = Ur UE eg = aura, ‘gp 1 pantasqo 29 11s ‘| uits tw 2 UU, = euros w-= tw anes y= ats ty + at (qs Hoy an-= th )- ate remem, 2 Ps pausgo 2 ory nos 30 sofhious m9 (g/=uy pur = wv) se] won 2m) FOEKOTL a A Adoosousods sno} or ae Aanpuaye porsyg fo 00921 Se438 A Textbook of Physical Chemistry Interaction with The ene expression wt be given by Nueet Ve gilgmB + ony, + mm ++ td the resonance condition is given by Wye £162 + img * amy +" * Oy aay) The sumber of mys given by te reaton 21+ L,where Ps he spn gut numberof the sults. This, the interaction of et lec Wilk nea ives eo sons, wee N= @h+Qh¥) ~@h,+ 310) ‘A gece of meres ith mentioning her. Tiss when all te n prs aida i. ay "== ay The fesoanee conti Molecular Spberoscopy 439 BV Big B amy + my + + my) aay If vis held constant, the values of B by the expression Bm Byw a! (my + mya to + my) Since fora proton the permitted values of m, are + 1/2 and ~ 12, the sum in the above parenthesis can have (n+ 1) different values as given by prem eee (eel Barbe GE-5 ‘Thus the expected numberof lines are (r+ ach oer. Te intensity ofan absoptio ly proportional tothe degree of degeneracy of the involved levels. The relative intensities may be computed from hich absorptions are expected ae given ile ml 1 The above scheme my be ilustrated withthe example of p- '* ‘The benzene anion radical may be prepared by the chemical reduction of benzene ‘with alkali meta in an inert solvent such as 1, 2-dimethoxyethane or tetraydofiran. 6: 15:20: 15:6: I with a hyperfine spl semolecular orbital which has @ node inthe plane ofthe mole carbon atoms have zero-lecron densities. However, this n-electron clectron pairs of C—H bond, eausing hydrogen atom to have a some unpaired spin density which accounts for the small value of hyperfine spliting constant. A useful relation between hyperfine spliting constant (a) and the unpaired spn density (p) on ‘he carbon stom t0 which the proton is attached is due to McConnell 84 Oa where Q is called the spn-polarieation parameter. For x radical 1 For methyl radial, the value of gc will be equal fo one, Hence, the hyperfine spliting constant of methyl proton is expected to be 0.002 5 T. polarizefaveq pur gs Seo 29 I ur CaamIeq woneRedas ayy “suoosd wopetnbe ow JO faosaed op cv anp sou 2p OWL eS Aga ee 20 YALL "| Jo uoneneds aN ‘ sonesusiy nba jo (@= 1 +72) sou 30u cn yn Tvs 20H YS ON, 200, 1m $¢0= 2 7/1 =1) sro waqeanba ow por (im cot 52 [= 1) snopon Ny, 0 Sou. sped Jo urd sa Yo uBO} 2 OPA 9 Anon 292s ang or ao om Sau Zp U0 oe SAE Ua pee hu soquinu mmuenb Yow La OZ = *P PLE LW OT (erta sou aumsady om op soy weya ay “Lu é ze wo panu2o wnmaads san uz ‘ur u 9'Z soEKUaD ZumAds YoU sucosd wapatniaaoU on) BumURaNOD Tepe ¥ a3 eee, Lceeo= i axe amg = Ay 9UI8 WON x se99)=44 = AV 1 «Ol * 2086 = mHD OES =A Fy. 0t x 1919 = tan 2046 8 Fondo wowanoods © ‘ok pnom eM EY IY °S ZOO Jo anTes-F vey 2H°D UH panei, OL €1 PEEL ,01 x HFA SEE poAOHD “Ly.O1 x ELT = (216500 (LOL SD= "0D =» samy zr6800 5 omy ,629710 20 JP 9 5" sUOGID Jo oR Wo KsUaP UNS VORDATP- mL, Lol coy (60810) 1 01% 50) 909 =o ‘so03q 60870 ‘nym S780 90 PUR gp *T suORRD Jo yea UO AasUaPwHES woNDefo_K BL, OM @ = Mo ‘wonearouwe2yy Bsn a pamuupse 29 we suord yo spur oma ssay 30 sas Samandsauyzedy ou, suojnd Jo pur poo ‘gy asa Jo ue pu todo an “soup suovoxd 390 SuIUDD Woe ‘SvORNM 1) aap Svondsge ang apy om Se auaTeNYCEN, Teh Sdostomeds s9no2y0y4 vonnies very ordusexy 4 t a eons day ALU us ast Lat] srndenurl anit tut ditt] toy joa ua jo -30 3 cot onan oped 27 toad nok Op sorase 4S seterur-turt arrt) att} rin] arent tut 11 seututdurambrty buunatednitii austt ‘swore uoqies fp » 0 anp simasuos Zunayde ously yo Sones a pala ’ CO wh 8 soo8 avopngdeu ur soe uogio Jo Buaquana aay estro= i 0 seRoefou pavnoooun ea H uondosge ys Kuew oH Pep ordwexg owe oypes suounbyassomn jounspods asd eer 2a Aasqucyy poqstyg fo yooaran ¥ Orr442A Jesbook of Physical Chemistry Example 4.3.5 Solution Fig. 439 Example 43.6 ‘Solution Molecular Spectroscopy 483 5 ach of the nes = By + (0224 mi) + (0.268 maT) (42) = By + (0.626 mT) Byy= By + (0224 mT) + (0.268 mT) (1/2) = By + (0.358 wT) = By + (0224 miT) + (0.268 mT) (~ V2) = By + (0.09 mT) = Bo + (0224 mi) + (0268 mT) (~ 312) = By - (0.178 wT) 1 respect By = By + (0268 iT (12) = By + 0.134 WT) Byy = By + (0268 miT) (- V2) = By ~ 0.13 riT) By = By + 0268 0) (32) = By ~ (0402 iT) The relative inesites ofthese Lies wil be 2: 6:6 2 respectively yy = By ~ (0224 mi) + (0.268 mi) (372) = By + (0.178 mT) y= By ~ (0224 m1) + (0.268 mT) (U2) = By ~ (009 mT) yy = Bp ~ (0224 mi) + 0268 nT) = B,~ (0.358 mT) By, = By ~ (0224 mi) + (0.268 aT) (~ 372) = By ~ (0626 mT) Predict the appearance ofthe ESR spectrum ofthe ethyl radical. Given: a 0.204 wi? and a(CH) = 0268 mt. Fig. 4310 For idetical protons, the ESR lines are observed at hv ee ays tmnt ma + 4 By > : For mete protons ay at he vis of, Od. Hent te tes "lave imate 1:2: Till ebere B= By +0204 wT B= 8, By = By 0.224 mitcg =4 3 ‘pou wun raaano1 aos ypR gaye PoE Bue URNA LL sa pur OD wo suoneyroj Suynoyfos amy wos} woes aq eu 30 anes JO sopio ormurvonde a, vinisuo> jouramios amy Se wanoey pu 7 RY = eH eye) ‘eTTOSr s+pra= orth (orig anya yo outa 3 uP 1a orn eciosr ene aa any 2m oe Ken 206 : sare 8s (ve ba) sevioer aeort ee votssardxo ap wont axe soxfiou yenowmox PEMOLTE SUL, ‘ayesoualop proy-s ae sjexoy ABious ep snip pue 10794 wmOUZe/ABuE JO suotjooup worap aay aney 94° = £203 Avr *@so09 yewoyeO2 Jo wou ures Aes saxe 20np aay) ponove SUOHeIO2 ,"woRyO) JO sex 3U9:9HP ‘own sng pu wurqwanonr rene JO suOND@IIp WONANp 29.1) aney Om T= F Soa '2 = 7 pi | = £20} so}204 wmtzMOU NSW JO SU ‘my sep pp aang mrous%op axe st men 24 uo Au spt (1+ £2) sa poe aoeds so;9h tmmsuou ys 1 (1 £2) 2nny wD B|MOAFOW ESM, Shh Kdossouszds sno2i0N soon T¥Y A ame fu Jo sagen po 21 “ummouou j9Bue Jo wouedwWoo? Jo snes peo ne Jo mouedino> 249 Jo uompuoo uonezAueNb ay Aq pawIa Se sIEALO Aannoayos ay Au anay ube nq sands w Wonsoxp Aranige fue 9xey IED 01 vauamnou jaf a ynenb aed 1200 ‘vonmor Jo aueyd a 1 Buoye ioe yor woRDoNP Ue SY, Uo 0s pur ug 2 30 ue 0) Spe ouves 2ynoojour 0 wom pue> oxy, fanuenb sora © 34109 rr) “0.50 wurquauoUs nue 30 sy 2A ym ang AoA spONE Lremigae Sue UA 2 Jey) suvau wimyusmows sejnzue Jo ba 4a waats se opsaxdhe Aatoue ag) 128 of “(yy) bg ut (G''9) “ba FunMNSgNS wo sm, wer uot {6q vou ore sonqea pezmuenb osoya wmuauom synSue om 5177 24 Tt 1 tye v) pe ety ea at pret ve) [Rotsseyo aq UH wumusmout eynaue Jo oRpUOD U. 4 pourergo 9g Seu (T''y bg) uowsaidye Azoue Sw 4 tw vy) af oy “ar TTT q vend aonpes af aay ater fq wo8 Sy eareut Jo mouour ou °¢*¢ “1 ‘9 Jo sonpee year axey wed yom 2>qu. “umuenb feuornas ps1 p pue ancojom 24 Jo ebIoU Jo owoM omy st 7 AIEy 138 vy) apr eee spr AP aa ssoxdxo ama oar axe pue paznuent ‘8 sojasajou a1uorep Jo sor8iau9 [ev ern Paun09 are YoTHM (SON 2p Jo Sse 3 om BuxsegTo9-quump © Aq porzosaxdor yppour owes pis ¥ K asofous ae Tones ut sepoofout sore Jo sefZo49[euontY om 1s BuMEDP ayy 1007 fevonsiog 1 foesoua60q se/610u3 reuopeioy souojssaudea asspuoyy yorsiye fo woaeL Vee46 A Textbook of Psical Chemistry Carbon monoxide For CO, rey 113 pre. The reduced mass is Hoy = Patt = (CBIR 6.023 x 17 )H(OO16 Hg 6003 x10” Ince (ODI2Kg)/(6023 10)} + (0.016 kay (GARD x10 14 10 kg, ‘Thus, its moment of inertia is 1= P= (1.14 x 10g) (113 x 10 mi? = 14.510 kgm? A (66261039) Bele” SG IFUAS x 10g m9 ED 1932 x 10? mt ‘The value of rotational constant in joule is Bho (1,932 « 10% m") (6,626 x 10 55) (2.998 x 108 ms") =3.838 x10 5 ‘Hydrogen bromide For HB, rn,” Hence B= 14 pm. Thus, we have =e. os £(0.001kg)/(6.023 x 19”) (0.079 9 Ke)/(6.023 x 1025 0.001 g)/(6.023 > 10} + ((0.0799 key(6023 x I = 1.64% 10 ke Jae = HP = (1.64 x 10 kg) (14 x 10 $3.26 10° ke m? A oe (6626x1074) ane ~ GIAFG26x 10 ig m9 IO TY © 8.595 « 108 ar! ‘The value of rotational constant Joule is Bhe = (8.595 x 10? my (6.626 x 10™ 5 5) (2.998 108 ms) = 1707 105, ‘The various allowed rotational energy level for these two mol in Fig, 442, sxe shown populations of energy levels can be computed by the Boltamenn 2 = exp(- ABIET) (448) And ny are the number of molecules in the lower and upper level and A Bis the energy difference baween the two levels. The pop ineach level is given by the expression ny exp- Ey/kT) (ag Molecular Spectroscopy 447 se sas jews 0 res sett ee i ue some see i — Ana 2 4x04 5 is ary] i vot} ye a a eas wath a a it —— =i , $4 to = vee Since the molecule can rotatein 24 + | different planes withthe same rotational ‘energy, the various rotational energy states are degenerate by a factor of 2 + | “This factor is known as the multiplicity of energy level and is written a8 gj. The probebilty of occupancy of these degenerate states are completely identical and thus all the degenerate states are equally populated, Incorporating this malipticity factor in Eg. (4.4.9), we get e006 8) a0 From Ba, (44.10), we may waite Be QE DEMCEMD ID sap agury (an ne OF #DespeE nl)" GD where J’ and J”ate the rotational quantum numbers ofthe higher and lower energy levels, respectively.‘aqnogons amy Jo won 0 Kuanbay mp3 no st ouow 2d YO wouodio 2¢p Jo uonenony Jo Kovanbay au, "p yp 315 u wnoys se Kenypousd sorennony soded so aed 3 yea waa BUT 1wonuow a0dp Jo woo spua oage8ou poe anysod ap "uonmos aqnoaoure Jo uonsor om Aq pred es 2p 30 Kouanb as am aoduio eauooye Hanes SM ropuadied ave ‘vogeipes amp Jo wauodanoo jounooje HU, =|N0R]0U ay Jo LonENOs ‘2h pu woneiper 90 Jo PRY Wowno9|2 Bunenony. spel ayp uz2a0q voNDESOL 24 249 Weonp st ajoaqou Supe xp pee "Vp a1geL, tt popuosas erep ayy HH wouoasBe UI Ose St ANTE STAL, L = eep=c0-eeL= P- ary an = can sora 080410 2 ae o= cap jaa+ Bae Gant + Araya e 10 o staan + prev 380001 + ro) on SL o- [ava 5me p * Tie ane a smu fst ova sus ‘2 Bums koxp pue fo eodsas qua (OL) ba Sune ‘6q pourmaap ‘9 veo sopnooppu jo soquinu umanews Buyary (PABoqN w2xe2X) F JO ene OU —r ao Wao et 9 9 ze “a i's 380 a Gr Kdossoursds somo2y0n¢ are oro ae 0 sao wo si90=golz 6 a nor evo eomaet at a rs eco seassaagst se a nes wo sevosmazer ee u west asco ewr-ao az o ore revo = 806 6 6 aoe uso wor=ats a so e650 eeriz= 49s st vas v1.0 seigl=azy vice ovo ust = aoe 0 sore oso 80 9¢= 400 6 wsv9 680 w9r= act L war $060 eo=a9 s srez 60 slaaz « eo) ' ° “se (9/9 io (se=% fF aa Joneyou 0 “or sequin wMUEND & s2r1n uosoyyp 10} 956 18 09204 141" -Wx9 jo anIEA SUL YF IGE ‘ro anyea aun suede suonendod 2140 ol utpundsaus09 ap smous Ey ANALY TOL X BCR = | EIEIO pero aus YOM 30} (9 UO HONEAD|eD Jo Sys SHY SLEEP [Hy AGE “soseatoopy unusow ain WBnonp Suyssed Joye pur oq ayy saseara sno] snOUEA 29 Ut (aA = oy adsau YM wopendod jot ay J0) sojnoajou 0 xoquiny ayy “SHOPRS Oxy 25949 Jo aouanbasuED v Ausyuo postya fo yooursa, v $Y450 A Textbook of Physical Chemistry Molecular Spectroscopy 451 ' ' ; Jo folot ee ! meee Pott “ anceot (44.14) els When the frequency of fluctuation of the component of ‘ > frequency of rotation of the molecule) becomes equal component of the radiation (the fequency of raaton sel, there oa han on absorption li. I fat, in Table 4.42 are observed, pore rotational spectrum would consist of mo ‘8 sezes of absorption lines atthe wave numbers ‘Table 44.2 Energies of Absorption Lines in @ Rotational Spectrum those with no permanent dipole moment ane knowa as microwave inactive molecules, » ‘The homonuclear molecules suchas Hf, Ny, O> Cly et, ave no peamaneat w moment and heace do ot exhibit the roational spectta Molecales having @e of symmetry do not possess permanent dipole moment and hence als fal 88 108 Solecticin Rule that is, the change i the rotational quantum number indsivng ie selection rile for rool ci 7 ‘The spacing between any two nearest absorption signals is ese transitions are not equal noted from a given level depends on its population, ‘molecules that can be promoted 10 the foot of Fig. 44.5. There occurs a progr boginning and after passing through a maximum, it diminishessou, um ycioe=°az pur wo perme = Ptgg sp uaa axe 394 eo anode, you F Q9On-ZT UE, JUN POP Ogy 3 S065 '¥ Zr 990 or pund} S| OD, 10 vorsbosgeTeuOHIO! sommsuatut vondaosqe yo uostdieo ayn wos ovepunge axe OH osTe 19 10 ou sd} uorstunsqns a:donst sueadde 7 204g ‘2qno2]ou 24 Jo eM! Jo 1H9BON yan suena uotwoW ajodtp sp pe Lonmansqas oxdosE ap KG 1p s8a]omuEW yeomay> 9q 01 punoy $1 2]n22I0u1 jou ¥ UL HOT Ayaan red w UY, $1 anaotou O39 3051 30 somyea a, esp Adeosousads somom0H1 ($3 01 x 866; 4 stop w=] MON 2, 01x SVT = C01 x 9299) saa ‘9 ‘sonen 219 3 gs BS =) sopon AES = coms 18 OX ZITST= mC 1ST = sou peg TEE = ae = 8 ooueysig ‘2A 9 ‘SmyL @01 Toba st SIE, OY ZH puog oujwuar9q, ‘aoods ouput 20 8 ap ojnaotous QO Jo 959 al ‘afGuERXS 3052, z]mosIoM oY uuNZads OWN ee eye, GF oyuowesp © o cours paog ap oursirep or posn 29 ue nares uoneos my, JouRaNdY ee i T ejay mayads aon i ready srr casuony porstye [0 Youre], ¥ 2p454 A Tenbook of Phys Example 4.4.2 Solution Chemistry 192124 ‘Thus ee 18367en? * (12.0000) Solving for ‘The momest of inet nd the period of rotation energy level has th highest Population at 298 K? (e) What isthe change in solatonalconsast when Hs replaced byD? ‘The diference between the two successive energy levels a given by Eq, (44 or B85 em"! 845 x 10 at Now Bis piven by (aT where fo Bris = 142 x 10" m= 142 pm (6) The energy ofthe rotational level for J= 1 will be B = 16.90 em! = 1690 10 mt ex Serpe 23357 x 10-27 Molecular Spectroscopy 455 ‘ron classical mechanics, the kinetic energy E, ofthe molecule i given by Pera 3 where isthe angular velocity in radians per send, Hence ion of H by D does not affect the intemuclear distance of HBr but changes only its reduced mass. Sine B is inversely related to I, we may wite = 4278 emt (2) Show thatthe frequency of rotation (=) of sgid rotator increases with increase {in rotational quantum number J according tothe expression Pre ve pa VID () The increas inthe frequency of rotation increases thee ‘fo move the atoms apart. Consequently, the bond length of dit wit neease inthe value of Je behave srg rotator 8 nowrgié:ottr. Fora molecule executing simple harmonic motion and bebaving likeTF OR B= Pig Oix iT MUR AA | oy peNoneses] 1" A 1 HN OL see = Gomeorxsoe) WH BEORY OT pix Ear a pian” on swung oS -o1xse1_)_ ah wi epiamyorxewis (eet) th, gmemgancaris (SEE) Hey om go eo) 6 60 M1 ,, 01x Jee = (8001 866) (MOT LY LITO Chg 01 299) 128 a Fanon tn Bunnag 24,88 21,88 2H atom AEE a g sous me EE tan PEE gc mon it Or HOLE 19 EL = sof amc pur g 3) Busos, (oe 2 SSETOI n> ssc TOL = Fal 998g ilo prcygs Pearse Ish Kdooromeds somomoyy (+p = DeT~ (1+ DEB) ~ (0+ 0 +N = (0+ (1+ Pa) = ig -ig egg @ : 398 am ‘(z) pus (1) sb Supenbq Agure= ase © eee eee ee T 4 wand s poaous ap 30 ABsova anoury ap “ofan eye oF BUNpIO09y Bem ap son ay ey mee om wang ae om oO ons oj mn mos (ep Bog 2H) pod Jo rr> 2m) a O08 yee pie snduo tn Ag san 8 pu yuesue> WoRIONp ERRGENEDD Se UMOWY St IH uonnios _Aussmey wri foYoOmtaL YO458 4 Texbook of Physical Chemistry Example 4.44 Solution eat atom moe 'N and DCN, rom the following fats sbout HCN molecule u——c N en Fe Keene by Se conto ity ‘we may write Balancing the moments about the cenze of gravity, We get ; art Mer = Me Expressing ry and ry in terms of re withthe help of Eqs (1) and (2), we get alte 0) + mere Mylrea re) ures — mare Mow — mae Img eg me where cs = + Met te “The expression of moment of inertia is ° Tnen = mri Expressing rc and mur + mardy +2 (mg + me+ my) + re gre — My Fx = mardi t meray + FE mye + Rel em Fen) ing ror Eq, (3), we gt en = my a+ erg (ests 2 BE) areu ~ muro the requited expression of moment ule, the coresponding expres all, We calculate yey a Foc 0m and Bp espetvely. The rotational consan in frequency unis given by B= h/BxI, Hence, we have Molecular Spectroscopy 459 hao BE in! Trex wt oe te 8x? Boon Subscting the given data, we get eee F (asaiso7 ioe = 1895 x 10% Fo = 1.895 10 kg 1 Gemma = 2315 x 106 5 se 2315 x 106 kg on? a 107 kg mot 35 Now mys cl BBL 165107 6 GOOS% Part "NE IO ° 2 2X10 KOI a9 0% rig = ZEIGT, = 0382 10 tg 2x 107g! © 6023 = Mou ay 16% 10-™ kg) By + (2325 x 10° ig) ry (656% 10° eg) Fe — (2.325 x 10" hp) roy? (166 + 1993 2325) x10 ig 166 ray = 2325 a8 1895 x 10m? = 0.166 ry +2325 ry of BSI m? OTIS ry + 502 ry +077 re Pow et = Fey We have a3) by 2 and subacting from it Ba, m= 463 1 624 x10 463 Now substituting yy value in Eg (13), we got LAB ry (1.79 10” my ry 348 X 10°? a? = 0 Multiplying Ea, 624 16x10 m Solving the quadratic expression, we get(yr = axotvw Cy) = faxzytyt— {98 am ‘sun, uouroo a u|2our> pue suonenEarayp ayy Ino SUES UO . iP (ag) s00 ('y—")9F- = “tape vp (one) 909 (VW = Gags pan 1 (suonoury amis axp asm Syenbe wea oa) svonyas s¥g 4p 0g 203 anes ues om sey A Kova wouagpp ax Sau 8 paw 10 saqduo iz) $00 1p =" won) noe von8 woes a 30 ase aq) Joqy> moo} 2 pue'x seEupIONS a, : 0 a ee as» (x tye He es — "y= te ose cs y= req a vo BZ" 10) SURO, ‘a am 6p tg ur unoys uonuoAvOD US aM puE Me saYOOH 01 BuRPUEDDE “MON Peay = 209 amy wo Buse sa10} SuBOISTA ws 7 sy) 1a = | eq amy vo BuN>e ao10) Sues ney am “ney puoaet s,uonnan a4) 01 BurpIO09y ws) ly = te = Buds an Jo vorsuarr, ney am “ury,“15'p ta w unous se sg om am Jo stestane|dtp om 2q% pow rT =n 5 a4) Jo aunseots ; sub sy 7urAUOD 2010f a $e UNO HE|SUOD BS AIS soy doscouzeds impo owner poanp s eq ayn 00 Sune 20103 ‘mores 27eHSe0 oworary y ‘xy waw229|dsp am or revons0d« [soy ow “yore 0 Zuypuoane nnedou v soy Hot porsouuos a 2 2 he wonaats q “ocio} Buoys Jo suonDanp a a>-PUL swoure panop pue swore Jo uonout Jo suon22xIp ay 21e2!pUY sMOME pros ntoy pus wauaoetdsp Jo ORDA anntso RQQQL LL & ‘Suuds am Jo voysuareg (14) rH HH eQRIQNIA p ‘wonrsod umpggmbg (+) BH mH UL ‘Bupds ap yo vorssaadwo;) (4) we ennongoes ogy He 4 dy By TQ2QRQ99> © amide an 0 oon 0 i) fi angoogvos nisod wnaganbe ‘smozjout onmowrp © &q pongmxe woneigts eaIdG ap SoSH Tsp an ooo qureyp © ouoqeaqu Zunprans ropoumis sy ag 20811980 DIuoULeH Je Kouenbas reaissei9, vuogonponu SITNOTION OINOLVIG 40 VLEs TWNOLLVEEIA. Sb Aaspunyg raishyd fo yooaraL Yop462 A Textbook of Physical Chemistry Classicat Potential Energy of Harmonic Vibration of @ Diatomic Molecule ‘Wtng the above equations inthe determinant form, we get | mOn my & m(2nv)? ~ ky Jn order to have nontrivial oos of Ayan Ap, we must have Wh & ma QR) ~ by Opening ths determinant, we gt my, (2nv)* = ke, ORV)? — kem, Onvy? + kena kPa 0 or mymy (nvj?— bem, + m,) =0 ow ved [de 2m Yorum, jComym) 2 Ve Where {= mmm, + m) and is known as the reduced mass ofthe molecule, Equation (4.5.10) Aistomic molecule u =0 45.10) he required cf rge harmonic istic frequency at which atoms of ‘The potential energy of a system at any instant canbe evaluated from the expression san Tn the present case, we have av whee Ta oe Wak Arden) On integrating, we Vek +t 2 ‘where 1 isthe constant of integration whose value may be determined from the fact that at Ax=0, V= 0. Thus /=0 and the poteril enecgy expression becomes Vad han) 45.12 of potential energy with displacement is shown in Fig, 45.2 peaking, the molecule can vibrate wih any amount of potential enery, ial energy ofthe molecule isa continous function ofthe displacement ibrium position, The vibrational motion of areal diatomic molecule is pgroximately harmonic fot a small displacement neac the equilibrium internuclear configuration (se Fig. 45.5) ‘Thus, from Ea, (4.5.12) it fllows that fora real diatomic molecule Molecular Spectroscopy 463 that is, the force constant is equal to the value of second derivative of potential energy V with espect tothe displacement Ax evaluated when Ax approaches zero, In other words, it is a measure of ate of change ofthe slope of V versus x graph ‘ear the equilibrium interucless configuration, ‘measure ofthe curvature ofthe potential well nea dhe equilibrium internuclear configuration. old good for quantum mechanically by solving the resent case the solution of Setdinger ‘equation yields the following expression of potential eneegy (0412) buat s.a3y where Yaa is the classical frequency of vibration (Eq. 45.10) and vis the vibrational quantum number, The allowed values of the later are 0, 1,2, -. ete ‘Thus, the vibrational energies ae q «the molecule cannot vibrate with any arbitrary amount of energy but with ony certain discrete vibrational energies energy diagram (Fig. 452). The down, * The energy levels are equally spaced, the difference between the two nearest levels ithe same throughout and has a value of Vay. aey If vand (w levels, we AV= {041 #02} hase ~ (0+ 172) Bis = hy, se the vibrational quantum numbers of the two nearest enetgy as19 Ber5y expiesed in wavenumber unit is known as vibration bol: Giz. C= Vike“ys ig ut umoys ‘are 709 Jo sepow reuonexqH samp ain SuMp wowow 2fodrp ut saBuEYS ay, TE ns seypousd salve 2a pg. endian ‘2yn29I0n SOIL ‘yoo pasoufiy am ou pure ones But Nowous fod wy aBumyD eA ‘ste oy pur uous ofodipyuaueued v atop samaofou op zalana0s39ft ‘spade ouoneg Sue mous you op Kau 21 a4Rzou parr areSajooqou YN ‘vay pur ‘wonesata SunonansfeorTeuNAGs omy Suunp ywewOU ofodip wy aBUEYD OO smgoo arp ospe pe Wanrou aodp azz aay samo SAMOTE| 1w2]2AUOOH bid dit fl you uoueuud © sey 2jaojou ay ‘Suunp yowouropod w pessaidioo pue poysians eanewnp st 2jnoycw a a1oya “von eIgIA FuTyOaNs [Roos “21 uoHeIqI Jo 2441 U0 Suo oxxy 24 'sqnoojour OLEP UL ojncojou amp Jo woneagta ox Burm uewow 2yoip ut Buoy. ¥ sn220 219 UY, quo pores sy aoqour © wos} poy jeasIe}9 SuneqTIsO we -puNy 2H ap to upmpe ao nebo ao uate ese BROS So kdostouseds someon ‘jana 204814 ay Jo Aue oxy ueypastorE} sour yom Saf Jo UONFISXD a wey apnjsu09 Ke am ‘SM as past g=a Woy ‘a9 puno:3 9m ut uonedod E uary amu; sword xp yey) ans96qo am ‘Sange PareyRoqe> axoge ap wo a x@\o= 01%) = 7 ecOT x 89 = (689719 = (CFO THAT gO XU DDO = axon snd 01% FE= FOIE = [01 < TPMT 1% 98 = N 01% 98 = (rHLOT-VH = (UF 01 X LPAL 01% 2 INO = aperouou voqins 10g 1 poy a “snsqour asa 309 uy “Sone an Band09 Lox yc 1 01 Tp ibe fm 29 pen pandas 24 eu! Sosa 2504 sauenig apreow0w 10 ou poe 09 1° Lay seqnoaous “aonmedod aaa) av ame : Gia" -)8x0 "y= 6 st wopeno oseurzog 9 ton se [aot fou Jo suopedd anes a, ‘sv a) 50 tap sonnaenb amp ti09 rsp porow aq Kew [oxo] ABiou> uoneaatawareou ‘ap useivaq aouateyy ABIouD ayn Jo ey sn st KBiou2 iwIod-omz a, peo 0} axqar sar ye 9q uso stHOR om) > Imp © yoy ABvous TeuoNEgEA wNuTEIA ‘Bsouo yruontugys awos 240 cod ur Aurenaoun ureuao one 01 5 ua9g anny PINON THEI oun aye) Bugpuodoe 30024 pu os 94 PINON uonIsod ap ut AunaDun am spurs ara swore amy 3 2ioud Srueyrooun Roques 2M 1919 Ktsagdavon 29 3982 2122 59 wou St ABIBUD S940] ST aN) Jo anos 9 soy mq sorm4gH =a) Bizus pouoruge 12m01 PL & 2 fo ase ays uy 50 0132 OU 51 (0 s0n07 A610u3 Jo woneindod, Onneron, asc porsiya fo xo0qreeL YF466 A Textbook of Physical Chemistry From Fig. 4.5.4, itis obvious that the Symmetical stretching vibration wi infrared inactive wheres antisymmetical and bending modes will be infaed For water molecule, all the thre vibrational modes will be infrared active a ‘ate accompanied by the change in the dipole moment. No change in dipole ‘moment (TR inactive) by the sign dh Dipote moment changes perpendicular ; J Fig. 454 ‘The variations of dipole mament during the three vibrational motions of CO; Selection Rule show that for harmonic vibration the condition of Av=e1 es 4 that is, the change in the vibrational quantira number is unity Equation (4.5.15), infact, the selection rue for the vibrational transitions (see Setion 4.1), iatomic molecule, the transition from one vibrational level to another “4 Molecular Spectroscopy 467 Since the vibrational levels ae equally spaced Eq’ 4S tos between aly two neighbouring levels will give rae tothe ame energy change. Thus, ofly one absorption line is observed in te vibrational spectrum of a diatomic molecule ‘Substitting Ba, 5.10) in Bq, (4.5.14), we get (45.168) (45.160) [Expressing AVin the wavecuber uit, we have ov ap fe 45.178 fe ~ me Vt re 5.1% Equations (5.160) and (45.176) may be used to determine the force constant of a distomic molecule For HCl and CO, the values of fy have been calculated in the following. Mydrogen Chivide Prom especies, we Fin at Ai =2 890 cm" The value of is po MH mame, (2001 Kg (6023 x 107) + (00355 kg(6023 x10 = 1618 10°? ky Hence = 4ne’u (A? = 46.14)? (2.998 x 10% ms A781 x 1? kg 8? = 4781 x 1? N mt Carbon Monoxide From experiment, we find that AV = 424 « 10-5 “The value of sis memo, _{(OO12kg)/(6.023 1 Ime * mg ((O012 kg)/(6.023 « 10 = L138 « 10° kg us Mav)? _ 4147 (138 10° (4.24 10-1? me (602610 Hence = 4 = 1.838 10° kg 5°? = 1.898 x 107SUL 21924 1 “one By urgownb reuotesais 2p sip 3ue ‘oye a7uoutzeyae amp jo Kovenbouy w senqea resfonuy soy ory soqurmu o9 fyaruouueyue Burpuodsai09 2p st °¢ ungaqqynb se snowy S74 598 ‘me §2y00H1 Koqo 01 se 08 one? 29 01 parepsuoo °q eur puog emp ‘waurane|dsp sm ump 2830] {ten ou st ‘129 sed 1 soqe $1 (pRYN "TPEV.T puog wnaqiTMbs ayy woH MowaDe\dIp MUSA aor's'r) +a)-a(enta)e"s ‘ey om wn quivers om of (war's) (2 +4)—-Deay(en +a) =" repuaog @ esion on 4 ‘jana ABroue fenaorod jeuoneaqhn pomOyTe SOLEA AW 10} WOSSOXDXS GUyMoHoy aNDBIOR J -ASsoue Burwo7o} ai $9418 uonenbo yueyesaY ai Jo wonnjos aieurxoxdde o4 oyworsig Bi po wonenba 2upoxjag u wossaudxo Aaiau9 oad asioyy 241 JO UoTINSGRS ABLIUZ FeUONEIAIA. J ‘a op 3o[anusSN SOyBTY om ‘fiou> ejoqened swowrey oy we ffdoas a0Ur S80. (55% arduexg 295) czy 4) Kq vont? sto tomsu00 nL ‘stave uonpossip 2x9 st pe 3[n29[oW JaJoqUeA ® 30} IUEISUED SED Alay amy 0 Krenv03 vers) a "o}ére- a =A orp £Bs0uD pom 1 Bupyeerg Jo UIs Aue ZumaNXD fy Kup any ueD suoREDSO 2zuowsEY 2372239 01 | pazeprsuoo 5. gory 2froajou Srmorep v ye SURLY SHY “anfea exRoWU 2B Se 0} oxo Jo anes wurwsra ayy wor} SunzEISonpea Au aAey UED (ETS'p ba) vuonesain, soqpnas0 oun » Jo uossandya A8s209 2xp uf ZaquuNY uIueNb TEOOREGA SU, squoueyuy ‘amma ur aoa paspisuod 99 Keur woes ‘soauaoeydsp years» yas pia "tA ACA] p¥eg xp JO 1050 Jed s{wotssoxdue Kzoua ay yomuapod aso se UO ‘5 pun asiopy ‘Wa 00 anp s1 uonPsxaxdde poo’ v 0} an B:ou0 enucnod aut ‘91 yon suojsandx9 a Jo 94 “soueIIpseojnUuqU ap YL 2|no}OW HOIEP 4 ‘Jo Aza Jo uonefauos 9) 4y parses uaoq anny suoSseudxS fends Aunyy —_PNUEYOY @SIOHN ‘sroquumu wurquenb euoneaqis J -AB1ous vonexgta 2quowsey ay) wos} wonersap 2504 pu ap swuauaoe| dsp mie] 39g (G1's"y“ba) soqunN umueRb fevoReIgEa Ut eseaI ‘mys saveaouy vat paog umginbe ap wo moweoerdsp wmanew ayy, td 9601 =a 01x 9601 = rex) J} 84 2 01 X STD, $Y,01 X 18LY T fy 01% 9299) * oy 5 8101 LAL = BOE HY OLX S19 =F OH (4h 22) _ way a4 198 om “(gT's'y) ‘by wong ‘9 =a "27 eae] TUOTENGTA a oy au eno [oH Jo opm yetopeaga Sy sca mod sno righ a « (Ena) Zth 2 oy coup ars9) ah 7 NSC meg HP my ayy i 10 fog "wor yo san a won ay am ope Jo apmndum ay 0 FuIe) «JO PMATY BR 8 en sommyoonr payor eo: (9% doosouvads snymomyopt assruony pars fo yooareaL ¥- $9_ 410A Texbook of Physical Chemistry Energy Level Diagram ‘anharmonicity constant. x is approximately given by hy,/4D (see Ba. 4.5.25) and A thas a small positive value of the order of 0.0. ‘The potential energy as given by Eg. (45.20) may be written in the form stir | to that af a harmonic oscillator (ie. Bg. 4.5.13), if we write Bq. (45.20) 28 V=(0e}) Ww [sie The above expressions suggest that anharmonic oscillator whose osciiation frequency decreases st say | The difference between the two vibrational potential energy levels is wend leedbse (ee Where and 0” are the vibrational quantum numbers of the higher and lower level, respectively. For the two neatest levels, we will have vevel Hence, the potential energy diference between the two nearest levels is well dp edb eed shyt = 25, 0+ 0") to each other with increasing value of v Fig. 45.6) Molecular Spectroscopy 471 ‘The selection rules for an anharmonic os transition / = 2. v"= 0, is found to have a poor intensity and is known as the {first overtone. The transition v’ =3 < v"=0is found to have negligible intensity and is known as the second overtone. The higher overtones ae too weak to be realized experimentally. The energies of the observed transitions may be worked ut from Eq, (4.5.22) and are as follows: Wv'eleu =o Aveny, Qvare v=o, ave2Ki @v'ese v0, Aves In the wave number unit, we have Mv ere uso, Qv=2ev'=0, avai @v'eseu"= ave ‘The transitions from v = 1 to the higher levels aze not observed unless the remperature-of the sample is high. Ths is due to the fact that the population in ‘v= evel is negligible at room temperature and it becomes appreciable at higher tempertures. These transition ae known as hot bands as they appear only at higher temperateres, The intensities of hot bands ae usually very weak and become more itense on increasing temperature of the sampleLo B01 86006 1) HDT £6 ot x eos) CEA wngar=4 Ft rss ea) Zoveyovo awoanetpe ue 20 (Bato rod-o7 sp 1 Bupuodsaue> sequ 18 86606 1 = % a8 am ‘44 305 Snes pow up gous 1 = Cz— H ops 249 Jo eee 29 Sumas zee L000 = tof an 3 05 uOS isos = 08 AULS861= eyaLe o mp orvete = CxE = ® {8 909181 = C7 onioso ouruepung aneu on, cynaou 0 009 cysosep a pr wes0o 250} 29 Aes Hod ont om m0 APRA ‘9 “Kouanbayy on rao ap rence éyaanoadsed 19 OC YZL € PUT Tuo 90908 1 AUED 3H Oy Ny JO SHORTED ORDA Ny PR THAIN ALL ae = ots Wl ETP TE 1a ry BUS cup Kdoasauzods soyn0o)0n1 axe acurepuny ap 02 fenbo 514 wor 1 jan yeucrmes sno jo ABs Jo uoyssadxa a =, ras prx ener = ES onnios oy 0 204 fe ua wend po ‘op oye 30 anes pourigo e. nye 2% Tag 4-™A= a fa woud 94 tw voxomog “loo uoreoosnp aan au uresfep Saou prvi om 30 woweG Boy todsas up nao}ou gp Jo ABreu9 voneoossyp ansend oooen o oes a ses unasea sey ABiouewoRE 2 ‘Sopos xnfo aisvonossp hv StU, yofour wow a 30 KBs ainooiont sogepossp ans Uno i209 SH sO a3 ns quota Gem sou evo ong eyo Absoua Freon xp F361 fy S5P9UF AOU ¥ 30 S809 wone208810 xs q02psK44 fo YooarAL YL474. A Textbook of Physical Chemistry Example 4.6.3 Solution The tay comesponding tothe disoiaton ene is given by iit 7 tae 5 (64.4526) Substituting the vale of x; we get 1 = i “2x 0007382 2 oem 677 268 Bek nN; Hence’ By = Ean (vam +4) ft (gu + Hel 2)" Yo [Yam + 5 Pp = (68.5) (1 903.98 ent") (1 = 68.5 x 0.007 332) = 649189 om! =64 9189 x 10° mr" Inthe unit of joule, we have Ey = (64 918.9 x 10? m“) (6.626 x 10° J s) (2.998 x 10 ms") =129 x10" The wavemumberconesponing oi ue eco point ery wil be even by B= By - By ~ 649189 car! 9485 on! = 99704 ew! Tae uit of ole, we get (63 970.4 x 10? m°) (6.626 x 10 J s) (2.998 x 10° ms!) star xi ation energy with respect toa of ‘The vibrational energy fevels of CO molecule i given by expression ‘The given energy expression Ey= 25 940 5 mol Hence, the energy per molecule i y= (4307 x = (2504 x10 (v Comparing this with the theoretical expression, we get ny = 4307. 10-3 nag = 2504 10? 132 J mot") (y + 112° Molecular Spectroscopy 415 0 (@) The force constant of the molecule canbe calculated from the expression wed fi ae = 1496 5 10° kg # © 1896 10° N (©) The sahacmonicity constant x, = 5.860 « 10" () For zero-point energy, v= 0. Hence (3)- =2153 5 x 10°] 0631 x 10 22147210 (@) The fundamental vibrational fequency y= 6500 x 108 et {) The fist overone cocresponds to the transition from U= O to v= 2. The energy difference between these two levels is = Bx) = 2407 > 10% B= (4307 x 3 x 5.860 x 10°) = 1538 x10" s Bquating 2ero-pont energy withthe classical expression of potetal energy, we get Dap etna «10% 2 fe a vag (24272201) _ (221472 16°)" om 610 Nm) = 4754 x10 m=4754pm(@ vd m panson) ney 2m ‘popison! (z1's'p ba) Joes owonEY mp Jo eI FE SHES SF HOA epee A ‘ny an una 2 io soap + (4 -Spv)dre oge-= 7 oy cine ay + (4 —oeldeepee—= ON -(3) °F Uap) aangan Y= pees 09g = “yochdxa oe = Syojda 9) ‘an 9 sg, -0.< "AeA erp os 01 pasooad pur o = "uUpi4p) 96 om My = 4 we ur FoRMogs DF pouorandor ag weo 2{n29jou aymoreip & Jo Kéz20 Ley Kdoosonoads somanoyy weston Ente Ee ‘you sed KBsove wrod- ose sex, ‘fou aed ova ted-orr aeureoudds “20H foe 01* 8907 (an arxseen gomaroer o1xs99 E= {6fiau9 wood-eua yex9 mn 51 EH 0D 8 vaod-ane omuvondde ap ateaney ayes|u sumsuoo Aypquoueyue Jey 2prfHt 10H sop aopsadxo Shoo op sv powwumsavoo ssato woRROSstp Jo aeA BONE lou £01 x 960't = °F = 9 = "aN wa users (2)1-(2)onse=s ers sx 01% {OUT = JS) 251 = 658) 096 52 = ime ae Ema) esr-(E 4 ™a) ono so tom 1 128 94 ‘vosauso Asso una om 1a BumNSINS () T Tier qua 91 anon} 69120 woysssp out or Rupeot Sot eooMEGES ap Jo JeqauNU uMUENb AU, (4) OLX $62 = (8919 “eh = on Ww (1 005) (1-9 fA OTX BE DIME 01 * 950-7) 80 = sma, fq.01 x80 =4-lg=4y xn Wy fay -yr0 = oN canta 980 (68 s070% Z~ D0 « L060) = C2— asyay @) opines psreiduexg asta woarsiya $0 yoorsas YL418 A Textbook of Physical Chemistry wetae = (£¥) (6) The frequency of oscillation vis given by Le eV Substting by = 28a, we gt Rearrangng, we get (am fi aaasuf ion eyo te mils by De Vir==)~ Wr =r) From the given expression of Morse function, we have Deb-0=b Since the minimum potential energy isnot equal to zero but (1/2)hv, we have @ Thedis Babs ivan 518 [ee 2 22n "99 (18.11 10° mr}? = 4119 x 1 Nav! Now = 39x10 Bax 60n x10" Thus ys [HELLO 23h (ii) Zero-pont energy Lye t = pave 06026 x19 = 264 x 10% Molecular Spectroscopy 479 ‘i Da b= Liv = 6280 «10-5 264 10% = 602x103 ) = 107339 ear" ) = 221094" 5,,) =593469 00" 21371 x 1 a AB, = AB he Sem x10 4.245.295 x 10%) Sexpt- ABVET) % expt (4 245.295 x 10 = exp(- 1.0254) = 0.3581 AB reeevra0 ABD 593469 eo ~ 107339 en! = 42613 on! 7426.13 x AB, = (426.13 % 10? en) (6.626 « = 8 464965 « 104) ™, 2 expt ae, HET BERT) = expl-(8 464.965 X10 the difference in populations of inv sven by‘Rp fox] FEoORRI paretvosse a Jo AEN AEH PUR {94a TEHOMEIGEL 3S9M0] 3Yt MUA patetoosse axe saqnoarous Jo you “23m duo) woor 3y ws "jso]yeuonmar pur '8y “ojdunxo tog oan ‘mp wosanda a somes ag ue, fay 2 fur KBiou3 yp, pares 249] oo) +4, az= gy 2H ‘sono of so49| roonmod manop ayy monala py agora Verse io ruoresq4s 980) “T+ = FV yn suo esgic en spreqqeooneos sao TM sn “1 FV SS monuia 19 Bal ow Oe HOE LED DEY shy 2m “HopISHEN Q =a —> Y=, OF ENED TT won = [E+ alex theg(E+ a) (E+ [Gre del (a+ n.fd~(140.08= 39 og nya squnvaren Joven 3 6 set SBs0U9 sod pe 240] vuopisue! ap 9g fa pe fA eT so wojssaudh steno] ony 949 woottog 22H a4, fy) Jo sroqumau uinyrenb feuoneos puE TeuoR i 1’9'P Buy Ur umoys se powuasaxdax 2g fu suonow yeuoner0s pu jeuonesqtsspoq Sunnoevs apraofou v yo (sou0 a Bumyp jeuonos snooumnums'kq porwedionae oq skvnre = ee “t tres oueyp uonenqza ® eH SiROTOG I PaMOTTE OW ST o352 OF enba FY SUIS sorBioue yrsoneo0 ey wodn SuIpuadapsaynp (e99) Teae Teuonesqy sures xp 0 Zur uojag sojaoqour Jo serious amp “sng, oF 1 F= AV go My = Py eet ‘soir oremedos ap Jo uns ap se way) 9g ews soy avon se ours ap age Suomen Yons 4} so] ORD} a Kp WHOS 2D fa eon a, 8009 1 sunny ons Zumignyxe umnoods unas 2 WHO en Yom sea ot AL Dvot UOMO! amp UF aBuEYD 21H 4 parveduioaoe oq Aqsnoameyuts Anat e Senet ‘noneroxafeuonesgia ap 0 Sypuodsanoo uoneIpes ai Sungzosqe Uo orton ¥ ; niga ae ern ee ar ars ea si (= 5 a)er— tha (Zsa) + 0+ ra =”; eso (ea)r-ipeEe) ory sang ao a on enn 805 ee ake ee aerate ‘S31NDFTOW DIMOLVIG 40 VLOAUS NOLIVLOU-NOLLVUEIA 9b 960 = 95C0= 1190 | (_18560~ 01.) - saeco ~ \Seer0~1ase0) ~ ‘ep Sigur unogs se sora fruonmyos amd Joep se dures ox tPA] TeUOTEAGEA soo} paveraosse sono] [RUORPION ay) UF s2IN9efOW! Jo, WOR NALNSTP ‘Aoior a pug =a urwoneinded jo 2omanysa ‘aver z =a pu [=a wr uonwindad jo soma. Isp Mivosaszeds sopom.on Aasyuoyey mosstyg fo 3009021 ¥ ORY482A Textbook of Physico! Chemistry Vibration-Rotation Spectrum Fig. 462 A typical vibration-rtation Spectcum Molecular Spectroscopy 483 Equations (4.66) and (4. ) may be combined into one expression as ~ 2%) (468) ‘where m can have values 1, 2,..., and so.on. The symbol m represents ("4 1) 4 incase of A= +1 and (J’+ 1) in ease of AJ= 1. Positive and negative values of mcomespond to AJ= +1, and AJ = =1, respectively, lues of m and hence represent transitions corresponding to transitions correspond to J“= 1 <- J”= 0, AE =28m+ tended i in addition o AY = ling of branches goes a follows, the values 0 and £2 at also allowed. Th lines arising from = AJ ==-20 = oO 41 42 Equation (4.6.8) describes the combined vibration-rotation spectrum. Since m can fines arising from 5p 4 aS labelling ofthe beanc s have values +1, 42, .. i follows thatthe spectrum will consist of equally spaced lines (spacing 2) on each side of the wave number ¥,(1 = 2x) as shown in Fig. 462. spectrum. The spectrum showin in Fig, 46.2 will be observed only solving spectrometer. Ifthe resolving power is not high, one wil dobsacve the spectrum as shown in Fig. 46.3. overtone) helps in providing the values ¥ and x, and hence the val constant. The separation of lines in either P branch or R branch provides te value ‘of 28 and hence the values of moment of inertia and the bond length ‘The approximate value of parameter B can even be evaluated if the rotational lines are not resolved, ie. from the spectrum shown in Fig. 4.63. ‘The quantum number of the rotational level having maximum population is given by bata a banal aaatata (Wa fee 4 44.12) 7” ape ~ 2 aan ‘This quantum level will produce the maximum intensity ofthe rotations transition. ‘The absorption line cortesponidng to Ve(1~ 2x,) will ot appear as m cannot be as bind centre or band origin or Now since m= (J+ 1), we have «(ibe *3) M1 J" 2, and so on. These lines are refered to as P ranch ofthe specu. “The lines coesponding to the high wavenumber side of bund centre comespond‘ynaojou 24) Jo sofa puog ut afuegp op a4foaur cary ba) ba BI, 4 Het rece av 2 40} wopeay} jo seaufop (s ~ Ae) Sururemas ayy, wonoyy pouownugy4 ‘ynao[ou seauuoN ® Jo 90%n 205 90m PUR cam anny am (+= £9) Home § 04, ~D%4 +E OEe~= ay 90H = BOUT MOORE OUOOHOAT TAA ef 0 Cel aE 94g stew o anuao si jo voniow ap a paguasap ‘a an (2 = 7.9) WOMEN O30, OCD RED LTE e692 08,0 12,0) 99 Jo UOTON PUORYISMER ys, wopopy jouope|SWmA ‘anu ai (694) ba wor (2) ‘uornios: 1-9 gz 8 saoumag s paw Q Jo ewnreu simauadioo wp a 2g usa uoneedas a 319 S65 ¥ DAIL 0} Stu yeoorms ap AIR (2) Stusvedos 24 Jo 300 a paquosop 24 > 3 su Ave wai ain 2q us uy pono s5ad0sno4 von SuepUR suoneia ae 2 soe asap uot dou 'so)epio09 Neyo [eto € = “faved ype Jo} ——_—yeyOUEpUN 8+ aah 4 ssveupiooo aan Buycads £4 poquosap 2q ue sored jy jo Bunstsuo> wyshs Y yo soquinn ‘4 wants sxyuera § poe 0 Jo swreew a weaning uonesedes 29172 MOUS (@) ‘some 2—= 920) ¢ 4,72 = mp SuORSUEN z+ = P30) E+ Fe = (e- D4 +uae == 39 4 ase 9 (unncads yon eeonEIGH Jo SIPEEG § PHO FD ZF =L9 ye o=sa—> 1=/a suns 29 40} gumuate o BFE am IG maNS (®) TP WHOIGOIE Ba > AL am) ** 1 paweurxandde 29 we drrooneas on) na we um fous 2m Sy LIAEf wD SUS SIE BUNS (0) +t eles haya atoge on onoy pe ayaa. am em 5 s09 2 a sal «{ Shahan nav pore ont souen Pur oye. a: YONI SE gz 201] MH, ‘ A(z sn sep gp 30 mae op azn vost aL, ae eh -[ OMA ati) a] fee reav q yw uaaning wonton a uy put fava 91° ue 9 “SOUL G97 4 4 c ~ore(e “ics 30 ¥ . “ar 2 z+ EA a ay ‘ ve pono 0 i Soyoung pe qo eUEU a av poe Say Kdoosanvadg somoq0py asruoyp poosty Jo yoo, ¥ yep486 A Textbook of Physical Chemistry ‘Table 4.7.1 deserbes the normal modes of vibrations of di, i and teta-atomic molecules. ‘Table 47.1 Normal Modes of Vibrations of Di. Tr-and Tetra-Atomic Molecules eee Tae a Ti dager aera a soni “nec “ta eat od Bede aw-5 wo aw» aio ary 2 6 1 1 0 Same sais cue Nestorian, 3 9 : 2 1 Sone Syemetic” Anima “ang “hectne Ws zy a BO OK Asignmeic" Symneiebn cre me) cman grEmg b=emo i Lnmericvsomis 4 ® 7 3 4 ee ee ‘ean Sean “a (cy ay sere) agers Lets Lect ECS HceCy HC=CH cet oie ms move in opposite directions approximately at ight angles to the molecular axis andthe valence angle atthe cent stom changes, Molecule rations of « small group of atoms are more vigorous remaining atoms, Molecular Spectroscopy 487 Since the bands observed in the region below’ £500 en" are characte ‘the compound in question, this region is kaown asthe fingerprint rego ‘of the fingeeprint region to conten die identity of the molecule with an authentic sample is considered to be one of the most reliable methods. ‘Some commonly enccuntere group absorption wavenumbers ae listed in Table 4.7.2. ‘Table 4.7.2. Characteristic Group Absorption Wavenumbers Bond Sg ca Gham 75603870 ca Gta ery cn ec Soos010 ce neo 30 ee 30-3050 ea iio 0 on ea ca ce ee ee ce con To, 500 oc weching 1780-1090 = wecehing 1280-1000 ex Sone wmcting 160-1680 rare weching «300 ow Ont cocane 30-3300 nbn ee wet NORGE seme 3500-300 Sa SH Seeding 2600 ac ae seeing 800700Te WONG aS, openbo a ot oso ose autour sjodip poonpot an ‘nuanbosu0) “egy Bly Ut oMUEA Sm. ">umN amp S17 pus vonpeL jo Couonbayy an 4 ars (uaz) mis 7 = uonents ‘29 0 Siypuoase 212M (2utsoo o) ous amp se SoUEA Inq >t wowodusoo TRoptoop sm “HSH apr amp JO waUodNoD TeouNDeO MN ou 2p peinput ue samnbor ose ajnoajou ay “uoppes Jo wrboq jo aouasand an Uy ‘jnaajou ap jo Agezeyod amp sp ina ao =" {quant st youas wouow ejodip poonput we saumboe 2qncojou oi “fpuonbosued} pty aun397 Jo apo pasey> Koysodlo axnrodsay 2 spreaos paiceme st pnoys suosoap patiayo AfoaneSou a pue Tejon poBtoys ‘Sennsod x21 pazaejod 5 ofusojour poy senso ones w 0 eves aH cn “mofo se poorsepun 24 Kruse anoqe ap oxy vos Buy 8 30 mod peasseP pono st pur sounisqns ap yo 9st ‘ovonbay waroytp 20 yea aus: a 3o swepuedapur 2q 01 puny “Kexneosor ‘Sou weuy pue ywoprou 05 pues y pue g sxuosqn ayy IH Pa-u= av aren ” se passodxa 0g Aru pu “yh uy ya}aMry an Jo (SIoquINUDAwa JO) sroueNbaN sty L9SMIOg DUE oH, 139 PY ay Ut APs BioyCoy Se uaouy st ouonboxy wep mn aU 4, peg pe =) Gay Mdooronveds som22}0yy ‘qootour 249 ur sdnor8 w2oeipe yo Sutpuoy amp jo ammeu ag nosdsar “a —'4 pur & + '4 0} Buqpuodsou09 1quios uv ‘souozex0 Jo aoueIad umsuoo 2a} 24940 i8uans puog amp sous ‘spung ays ue Due spuog 2jqnop ues Aauontax; s2yfty ye uondiosge sous puog =n 24, Dy > Oy > yl > Hf opin ap sayy doo ann so ssew poonpas xp 2ou8s jurexo 30 hoax om yo sseus poonpar ap vt 2searou yt sesea1p pu pg sip JO 1UHsLOD 2o1oy ur aseasout yun Sosvaroul Covonboyydnos8 2p ‘Snox yo a4 24020) sm, haz 1S ba) 7 open 219 0= f Sion 25015 ‘01 s2}08 Bs sm an pu 9 ag ssaqumu anes ewourepury 29 01 So 4e"yy t1=,a5teA yey cosa oten =rmemngg =a =A ‘ar soso @rouo ut soouasoNI aH ors ta) {{ci +0) —1} 4 (eA + a) ="E sy vossaudx £iou> youonmea oe opour feuoneAA]A B03 wees and 30} 9019 se oes yp ae enoads weuy TeoOREIAEA a 203 “encode muy ap waa ouniap oq uo encode uogeno aind &puRAoep 39 10> re enzeds uewey [BUOREO: NORD tora am uF papas are sey soy uoqumu wmuenb ud eof ost 7 aay SHOUD: 7 pp0: pans — ands pouoruy +11: ppO: pease wide udlorwefion ypduosye Buyurewos atp HIM “ounsedse “go + op Jo asamp pue Saxnodsay ‘gol + °A pue gor °A w snas0 %0 Jo umnnoads pue soyors ay ap “Aanbasuecy 1 = pl £0 J0 9500 Uy EQ = ot ata] (eooner saTewne £989 °COD pow %4 pm gg °4 we m0 S65 Kdossouseds sopooron, 5 404 s]a49|ouonsy a UY uoREyadod yaumugs Jo an1ua9 & Saxe SeyMD2fOU LO 40 pojounid axe sano 949 wos ndod auy uo puadop‘ensn TT] | | | ! sora sou sey som ss eipadgg ‘uewiey yeuonesai os 1 unnoods uewry juo}eos and pepodso EU, SOHO SE UNO mum sopou8 suoquinuasban BURY a0 PUP SBS 8 WHOA A108 song ee So toquumuonea Ye sou =a, "a yo} Jo JoquvaNEN ap SA sey euoneioy o:n, wn = tosrne: jouoneandc wopsaudeo oy A uon® soqumu as ye swod Sum] use Sm = ]a0Ma-~ 39 anny 962 = P= 9 1 UonDeps a Jos SUNS Gs» =f +000 = + Wl)ld~ (C+ (C4 Dd = ZV SH0y am = Yo = PV ag WORD a IO vv bd) (+0008 (+ Oa = 99 co von Jequinuanen Ul a¥aa4P a ryoa 4pra="J sy wojssaudxe Bio jeuonnes oy G ___,troaou au so uaumos tp 56 wus aunty SeIIX posal AaEgszERHOd E> wip ne ap on np #7 013 ag, “ou wou amp oF 982 SON ZF = PT ANH seinooion Yonsaye a suo Buses Bonny 2 ofa SDA Q = Yat VoNSSs os, sqwovela c zr pw g=ry av joenseds uewey F roou ayomp yo ensods uswy wuogres and ip 40} sos ones a, |BUONEIOY ong Anspuoy porting fo yout ¥ zr494 A Textbook of Physical Chemistry Example 4.8.1 ‘Solution decrease whereas that of anti Stokes li ofthe sample, As mentioned which 3/9 Eis crease on increasing the tempera le of Mutual xclusion Ey y= BUT + I) + (v4 42) ¥,{14 (04 ¥2}x,} The selection mules are 41-0, bye te as-4%) bie Bu; v=o Ay=-% Agni -24)-mar'+6; a0 whee the subsp «10 the Q, Sand O branches, respec ¢ wavenumber ofthe exiting radiation, Sake" hnes wing wavenubes By= Baby B= B-aky Bos Baldy Mach weaker an-Soks' lines wll ocur atthe same distance tom Ey towards the high weveruniber ide eet For actone a oral mode of vibration tat volves te sawhing of Gl Ramanand ined spect, The Raman 387 am when ‘wavelength of Frequency of the Raman tne at wavelength “7 * Sax incident ight of wavelength 500 nm is > Sx 07m ‘Change in frequency of we light is Frequeaey of ave oes 300x107 m S47 x10%m GOO Molecular Spectroscopy 495 ‘The change in frequency of the lated tothe energy dfeence beeen the ‘wo vibrational eels Henos, the wavelength of the cente ofthe coresponding raed absorption band is 2&5 500% 107 my(s47 aay 7x 107m) = 5819 x 10 m~ 5819 um =(2E2) 10% a exclusion, for molecules having centre le states tha paring Raman and infrared spectra of a substance, itis possible hether the molecule has a centre of sym hand, if the two spectra include comm no centre of symmetry ‘The rule of mutual exclusion may be exemy CO; and $0; molecules. The structure of CO; centre of symmetry. The molecule of SO, is notinear and thus the centre of symmetry. The CO, molecule has four vibrational mode the $0, molecule has tional modes. These modes along with the associated change in the dipole moment and polarizability are described in the following, etch —O=C=0-> During this vibration, the dipole moment ofthe molecule remains zeo throughout the viteato fe moment 1. Symmen ‘active. More precisely, the slope ofthe a versus equilibrium position of the vibrational motion, ie. the small displacement acar position produces a change in the polarza 2 Antigmaetic Sitch Q=C=0, Since during the vibration, one ofthe bond undergoes stretching wheress ‘bond undergoes shortening ofthe tond length itis expected that there wi ‘change in dipole moment of the molecule and hence this be infrared active. Since the lengthening and shortening same amounts, itis expected thatthe pola does not change du‘ing the vibration, More precisely, daldé = 0 neat the equilibrium postion of the vibrational motion. Thus, this vibrational mode willeT) oes pe ew mania ‘Sepowy UOREIAIA Jo waWUB\ESY Le eIaL “wep vont gp ut suonmigia sejorpuodied pur jaresed uo wopewuosuy exp Aq pouodds ‘ 58 UL 8% SARL, UI UNIONS os S| NoMUaISS anoge 24 ‘pazuEND ‘so, “f9pow OREN RUDUEpU (¢ ~ € x E =)p TARYN sinofous FO ae 0=9=0 09 30 amos 2 00H 9094 pur aur wourao 24a 1p pm9 Kew 9 HBO Wa SPEIE , "m0.99 U>A OH aanaeut (nosey F199 ) exrpeut amy wer eanoy ‘anon oe omg pasos PRET oajou FO 4p Aajooo8 249 spatg “qgeeae are exep oidasosio0ds Burmoyioy amp “OO 30 Lr doosouseds spro2}opy soqnoojou ayduys yo amouns aap Buxysges> w sqes anoge JO uuoyep wpBea}-pv0q AP eM 9H aap 01 anp st voRpi0> ony 5 Poe 9pt0 am oo} S9UN| UoRaLOSGR aN S3SE WOU OY w ‘ajo seoojou Bu1s¥os00 A S9580309P oxmugh jo 24 ynonsed 2305 au ueumy xp Jo woreezTodap yo aazFap a F) ‘uaus8 uy “uy pozuvpodop v sani? vonigts oueuruCsQue UE -ejropmed = 01 pouyjuoo 40129 qpauno9p i Sey YOK YB») Fyoxaeod feared 0 pozuyod wo: asu soa wontaqya surounss@ | rou st 2|noofou 2 Hp ApAFIUED HPD 2A MONLOD Ye AIO summvoo unneds paseyuy ay) uy spusq atou 40 240 twydipy ome ae jus uyaojoy 4p “o|e smn sopssaq “Skog paqtnsep uaeq sey aRo9]OW 349 ut Aoaunaks yo anuao ayy Bumysges> Spy Yry S| aN 034 3IIOU1 3p JO Emons 2 ourma.9p 01 popoo are enzeds jo sodA yioq “simon sejoefoUr B jo wonevymsoiap 241 ut Jayio yseo rwaua|ddns wsoads wewrey pue pasesjay uewrey puv pazeyyy ame 1 am “a]eaa}0u1 “OS apo» SUNIOD) ‘Knunus Jo anmao e sey ajnoojout {OO ayy TH 3H HP OD Sap 51 SIL Ftoe mary ssa pega uss 3 ansze pazeauy 5100 Jo pou PUOHEIGH © 9p 995m Sm, ue 2420 paxoyia 9 I 2pou uotedgi sp 30uaH pe Age ‘aq so8ueyo zjncofour 2qp Jo msowows 2jodip xp *uonou Zupudq aq) Sung, t ‘enoods uowey ‘Bue paves} souoneonddy QrO=y (mvueben san) spore Supe “¢ Aasqucy jooystyg fo x009%2L V_ 96498 A Textbook of Physical Chemistry Problem 4.8.2 Solution Problem 4.8.3 For N,0, the following spectroscopic data are available. predict the geometry Nf molecule “Wavenaber_ Infrared "Rann = = a (aR) 128s Aetive ese (golaized) eR) 224 Active ‘Active (depolarized) eR) “The analgie of dat & given below, Spectra contin some commen lines. Thus, we may ite of symmetry inthe NO molecule. Honea, the stueture of N,0 is N=N—O The asignnent of modes of vibration along With the reasons is given in TaNe 4.83. ‘able 4.82 Assignmentof Vibrational Modes Wane ‘Aisigemens oo reg 2m Ascetic eh Ig roblom 4.8.4 90 Bending isrequied for ond Beading For $0 the following spectroscopic data are available, Predict the geometry 0, molec ‘Wyvenumber Tihared Taman 319 1301 Aste) Active OR) (depolarized) Molecular Spectroscopy 499 in lines and hence the absence from the fact that noalinear 50> is /\4, The asignmen of modes of wbtaton along in Table 483. and perpendicular supported by the he given dat Table48.3 Assignment of Vibrational Modes Taide ne — i mee oN at eee wow es » an ge rages gs pees ee aia me ee ne = 3374 ‘nactve vs = nae ra 5 ese ro emiacaed apa the moleculeree ons ‘suomismen ‘wsogs on 3990 9p wep asus ano 9 I '6'y Bla UE se pL WREST, ygeqond ayy '6'p Bla wY unous se ‘tov in vf wopsuen og ‘uses ap suHEMaD voRezeGa= zeoqonteotut ak 2901$ sais atuonsoyo payoxe 24 ur woneredes eof gs, ‘peSunyoun sup wownsuoa 243 Sump uonosndss svojomussia 242 toy Krom oF s1n220 vowsupdy n40U2=,9 24, 1 aauig oqunu wyvenb Teooneaqys 99 uF aFuryD ap UO (SOIR UoHD9|2¢ oq 271) uonpmsayfestueypau wuryuenb ou st 2x49 “uonrsue otuonsaf HaNtT € 20, los doosonsodg sp22}0yy B ioojou pordnooo ue ous peore aq wo anoofou oAwOTEP& ut wOxD9(9 Uy, ‘uononponuy ‘S37NOTION DINOLWIG 40 VULOAdS DINOULOINA 6Y a 009 comp sete sin meme pose = ta Spl ator cmt i fa Pet —— hoy ee aces a 255 ee er $533 eee fS5i ey = eh Soe sepow jeuoneqIA jo weMNBISSy YEP oIgeL pq vu sm 26 gu Hoge YORE 0 Spo IP NEN H—-O==D—-H apne o smnas NE “pena 29S 0 a0 30 eta um wna foe co pea ee Fe POM mS usps poopy fo woognaL ¥ 005502 A Textbook of Physical Chemistry the excited state usually corresponds to a weak bond in the molecule. Consequen the depth tential energy diagram of the excited: internuclear distance andthe spac ‘smaller than those of de lower eect ig 49.3 A schematic Molecular Spectroscopy $03 clectonic energy ofthe mol dissociation energy. In the the excited sae is larger than the corespoading thatthe kinetic energy the excess energy in the of the molecule) is n0t asa) the ground elec 8 produced on disso ass! ‘the valu off ean also be determined with te lp of Blege and Sponer ext method where AB involving the neighbouring vi evn 0) = ABV 22 & v" =O) is pl nergy of te molecule fn the exited state.anu ‘2 jo wotGor auazeyip s2aqoaut uonenoxe stay se sapisuoya, eax ABN wonnsuoas «a —¥ () ave asa, “opeu 09 Sear sun200 9 YU UE ue ap pur vorysuen aquonoayo Jo 946 mn Jo woneayssep peor ving "aIqIS80 eomoerott Ss] uonysuen jo adh ayp pue pueq uondosge om u2amroq uo ‘S1WOWeAIOd ue xaydtuo> Axo fyensn st wnsnandsamp ap pass 2q Aew 1 sno = 1Y “94 uy su poppe 9q feu soyna9jour 2quoestod u suontsuen aqwosaa[9 aN mnoge SOU 2} Y ol pourngo 99 dem aqeaojout a4) ano4e uopeuoyr ya a2ou ay Sarton a6tp woHy esnIINAS aU PuE EI ENS OP ‘Ko "woulsven omtoaje Tusp wawiou jodip ut afreyo Asessa00u am Jo 358329 tq "ensads (uonesq Baynp aBueYD 108 Sp WowOU! aod jo wuouodoo se) ruoneaqia aind pur (quowour aodip wanewad ancy yu op 42m) amd ngnyx9 100 op sYoremdos (ON “H #2) ‘a Jo Alias woHe0s ‘jason sano.p 2 Jo stonoj ABzoua snows ayy 30} suoisandxo ABrou2 exp Jo diay om tH ‘vopemxoadde sounyuaddo-woq ap apn sed se an ur panoeqo ammans 2 219 ainoaiony ‘annupuoa F 2904 pw ajoaqou Xp Jo uonetoossp ot or Suipeo] vonexgs yo rane ov st 2jnsajou a Hay a fag sweesin | BE Senuoo duo yo sssuos aso sy wns ano aL, et Be Uno B PRL (oun sor oy ummm o) ayy BOR gaHEN OL g Pena s uanzof aj Paoossp st aynaqjous “y 3) ayaa ip Spannewaty $0$ Glossounads sons2poy4 Aassmuoyg worssyd fo Yooqsay ¥ ¥OS506 A Textbook of Physical Chemistry Fluorescence Fig. 496 Schematic represeatation ot ‘uocescence Phosphorescence ‘A photon which is absorbed by the molecule may be emitted as such and can be slsplayed in the emision spectrum. In this case, absorption and emission spectra are identical. In many cases, these two specta are not identical especially wher the excitation ends ata higher vibrational level. Generally, the emission spectrum is slighty shifted to the longer wavelength (red shit). This fact has been attributed the radiationless decay (or thermal degradation ofthe energy. What happens that the excess vibrational energy is transfered tothe neighbouring molecules during the inermolecular collision. This transference appears as the kinetic energy and hence beating eects are produced. When the exited molecule reaches the lowest vibrational level ofthe excited electronic state, the electron comes back to the ground electronic state and hence emits radiation which is of bighee wave that ofthe absorbed photon. The above mechanism is i 2s the fluorescence andthe emission spectra is called the forescent spectrum (Fig 49.6). The tine between intl absorption and emisin sof the order of 10s Dat a ‘Molecular Spectroscopy ie ondine Daaorecens| ns ofthe total spin angular momentum vector with z-components equal h/2n) and =1(h/2n). hs, the arrangement of two parallel spins can be represented by the thee degenerate wave functions (one for each value of m,) this canbe explained from farther apart in space (because of repulsion orientations of tiny magnets) than in the arrangement of In some cases, the emission of radiation is delayed (may be by seconds, minutes ‘or more) and ths results into whe has been explained by the energy ‘observed when for fixed geometry, the energy of clectronic excited states (singlet and triplet) is identical ‘curves intersect each other at this point. There is some probability that the molecule incersystem erassing where during the vibration it shits over from the Singlet toilet state ‘becomes weakly allowed due to the fat thatthe spin-orbit heavy atoms ofa molecule can reverse the relative orientation of pair of electrons.‘premoy yoru 108 ‘249 0 amgeraduiy an J sse00xd anne anja waies ap Jo amsodaey o> ynoejou Jo Kovantays am aBumy Yor 01] ‘sj ssonaldaanerpanvon £q uopedisrp ABav2 24, « ‘ars sruons2 unc apo} pagoea s 2tnsejou xp panupuo> st woneAtoeep TeuoneaqtA put worsieqt09 qeussqu! jo ss2o0xd S14], uoweansvap reuoneqe oun Kg Domo sooo woseue9 Teun Use aio “poysear oxo Je\pOUP Tp PanUMUOD s won: ‘idomoy panos 2) Jo a sa5S0 aes yuan pentox2 ISRO a} Jo 44ND ‘iano yenuared a ose pe sous auo ssro sano ABiouD jeHuaIOd ss0q yrpemou 249 &q sepidinon “oppoqjour ap 50 pono Apa s uomsuen yd [Bus om SRoe|oU Hos UoppIqIO, ae suoroefe posredun 0 poured o Faquime 9 sedi om, 200 Yoe9 S809 SSAIND Om 5 our 0 2hmo ABiouo-fenvaIod ‘uo way 3240 ss0x9 Ae ajoqou ap woneAy>Kep TeuOHEIgLA aN HNC « ‘ina00 (soue0sa1ony Jo uovewonoyd) uopeipes se Afsove Jo UoKsnue 9°21 ‘sox ear _poreagoeap st ang sypG>jevoneag Stet Saea09 an09 aonaai yo pod sm my 8; yon st aur Su, 09,01 D1 3029p tp Jo sr} yssA}OU eNOS 1 a ase Teuorejuen pu fevorMos xp se ARID yo apes op 33 pbx ae suoxs 01 98048 Ue UO, ound angempesnon ayy 5 (Riou UONEIQH JO UoARS 4], «| ‘are feqssopon Jo S094 Sse jeuonos Jo uonBdsIp ou], « ons Jo aBueyoxo ut aanooye toe ut axe sor Sjonnmps sy ssoo0nd aareypesvon ap q (Bo 0S doosonseds soymom0¢ ‘vod pray ayn papsooay sy rma any ‘ayo ubegeAjfensn 51 umnnoads ruoms9j 30 yeuoegI tp u AMINES aU soveis povioxa axe oi Jesu wy “PowoRou oq Ke oes ponox9 A} ‘uy wos A603 ‘81a Jo uowedistp amp pr enaods spon sip Supe yo uonedissig -{ourds wonsopo paredun amp yo aouasaxd 24 01 np) ars ‘snodord onoudew ip Zusmnbor pue (ojat ‘sao éxeay 30 couosand a uo spaadep 8 onaonsef punor8 ap 1 wanar#asne7o9 Koa 24) ON, Ao] PuoTIqIA pneu? 94 poyseDN Sey 1 v9 oy Sentmu09 “oes To} Wars AUN OF /BLIS Sp mous 2940 ssas9 wes ajaqou amp Caydn pu Zu) som KB OH 31 JO ‘wld Sussouo ip 098 a (98m 429 oojouuzyu aut 0) aap . ‘ts as parioxe om ul “uoRFSUEN To}BU o1pSuIs om SooNpUL UOROG uinsjoeds vbosge au, poumdx9 oq hom sousosroydsoud Jo wisunyDaN! aq MON quBosBIONdSOUg assqanyy postu Jo xooarret ¥ 905510 A Textbook of Physical Chemistry Example 4.9.1 Solution Example 49.2 Solution Example 4.9.3 ‘The absomtion spectrum of 1, vapour consists ofa sedies of bands which terminate in continuous ssorption at 499.5 nm. ly molecule in the upper sate dissociates into an groin state and one with an excitation energy of 90.79 kd nit) Calelate ion exergy of in its groun ‘he minima of excited and ground states is 18046 KI mal", whst energy in the excited ste? (a) Boergy of a photon of wavelength 499.5 nm HE (6626 105912995 108m") y9n cg. 7 (5x07) Excitation energy of Tstom (0) Dissociation energy per mol inthe excited state = Enemy of 1 mol of 499.5 nm photons ~ Eneray difference tetween the ‘minima of excited and grocad sates 023 > 10 mot") ~ 18046 x 10°F mor! = $9.08 I mot Find the kinetic energy of the hydrogen atom produced by photo-disocation of hyrogen ‘bromide wi light of 253.7 nm wavelength. The bond disociaton energy of 10364 mot Assume the bromine stom to be i its ground electron Energy cartied by a photon of wavelength 253.7 am (587 x 107m) Boergyrequited to break one bond of HBr = 6044 «10-5 6023 x 10 mot Kinetic energy of Hl atom = 7.830 x 10-6044 10°) = 1786 x 105 Solution Molecular Spectroscopy S11 ‘numbers which wil lead to the dissociation of the molecule inthe ground and excites ates. What are the values of dissociation energies? 308 cm, Calulate the dstoistion energies of the two states and compare with those obtined in pat). Explain ay diserepany. (Gi) Do you expect the molecule to exhibit radiatoniss decay when it comes beck from the excited state tote ground state? (i "The expression for the vibrational quantum number leading to the dissociation of Wemoleaeis Mee" 357 Heaoe \ rtd sate) = -1ams2-05 70 ar = TeTrmigs — 2 ~7022-05 1 excited ste) = tyr as & Mnexcied = Ty ai9 x10 2 OS = SH ‘The expresion for Vag Hence (6626 x10745 90 x 10'ms")0 6414 < 10%") Vag(ground state) = pawn = 147 «10 (6626 « 101593 x10 82 x 10?!) Vag (exited state) = ae : i 419 x10) 59610 x 10-71 ‘The expression for Vpis atin (1-5) = Lhe Yor gan (1 *:) pre (1 ‘Thus Vs an Ht (16414210 mt 21628 105 Volested sae) = 3 6626 x 107198 x 10 ms) (1788.2 108 21765 «107 1 5 Axis x10 3% 919 x10")poy anaudeu (1) pur “ameseduy an uM aia ap Booye wou 4 peass voyssanad som smnaaxe Joye tow anousew a 5p AUN ipewadod spear 249] ypoqUoyp us WPAN Au WodxD nO oC aumerodura sp 30 2oueoyuBs Ae ao 1982 ‘vo 29 ump pandod azo 9g ona odd aps oumesodue E41 [1 09¢ 1 sured Jo dd ants ote (rug yo = 240 8.000 01 PRU wa souarayip KBIouD a ‘neues Bosearouy of AeA weno & yo AB jenusiod oi 0p moH, huSrlq~= A Ka wan 9 pra ‘onoudew © Jo aavaand tp wr wrod © 30 ABsoua fenw=nodoghaty mous quoroid 33 fo area a st ry) ug oy uon Jo worssndya ap oy vorssaxa axoge 29 aq + Dip Mt S=0 ‘1.0.20 ywawow snaueu Jo vojssaxdve Ieomayoe weMUEN!) (4) ‘Touraw rsa amp ane sroqus sou ay a operas am aap ‘ney anoge in Jo sn FURRY wen sum parody (®) open wnsuawow rue jo uoperquen soeds ai Aq row nas op ‘sou ppo pur eyo pp ‘seu ppo pu ayo uaa, ‘seu vane pur i642 PPO cana sev poe 28ieu> ORL mp 3e sou PuoneaqHs xn Jo AvBu eM pasedxs MD BLE 61 = 89 €26 82 = Cos prmos8) ganey 3m, (HD 0.01 9299) (108 01 « E09) = (GoW § oumsgns 2 Jo jou sod (ams pop¥s) cr 9 €68 61 = Hb Bue 61 wo 192 6 = 04 (manos) 4 = (as pou>xs) ot PF COPE = JOW FOF x EOF = 01 €25 2) G8 OF Tye D1 ¥ 9299) (16 01 * £209) = (GN OU PL 6 TUS = Om FOr x 61L'S = 189 = y.01% ter 1 €209) = em post) “sonmuanemyp Sutaoros ain Buty yon 30} Adoosongeds yesfow ‘vor st oqumnu wnwenb us ap xR 21S (@) soueuosey jou AT2EU pur ase nsuBeLN a UeSLE NDA Op 1A ‘nouBeyy 429]onNh 2xoy yt 9m soumsges tp 30 2fout 900 0 % 965 = OLX S9LT~f MTETT =f ee 01 809T~f 1% 01916 = aes parex9)q7 1 LPT = Gs puna) sm, SVERGOUd ANVNOISIASY -™\=q AON f1S ossonseds someon) Axsruayy routs fo yooareay ¥ zis514 A Textbook of Physical Chemistry (©) The PMR signal of proton depends upon it environment. A les shield at low-end field and more highly shielded procoa et [Explain the above statement taking the example of (e) Whacare the 8- and sales? (@) Desctite the expected low eslution and high resolution spectra of CH,OH OH. spectrum of CHsCH,OH in acidic medium, (©) Describe the spectrum of CH;CH,OH inthe presence of D,0. ‘Comment upon the following: (@) Though the NMR spectrum is recorded at constant radiation frequency and ‘by varying the extemal magnetic ld, yet in most of cases, the chemical sits ae often reported inthe unit of frequency, ie, He. ‘The spin-spin iverctions ae Intramolecular interactions. ‘A complicated PMR spectrum inthe low magnet field is often simplified 32 spectum is recorded inthe high magnetic field ‘Chemical sift are dopcent whereas spin-spin interactions are independent the extemal magnetic field "3c and 0 donot exhibit NMR spect, (@) The potenil energy of an elecuoa in a magnetic fed is given by Ve eugbr, relation. ) Te vale of Bol magneton. i) Energy difference between am electron in & magnetic field of 3 000 gauss. Ln wha range ofthe elactromgnetc radiation does this energy difercace lie? ig the Boltzman distibution andthe shove energy diffrence between sof elearon, calculate the relative distribution of electron in the tion of the unpaied electron withthe magnetic active protons of oducestyperfine stuctures inthe ESR spectrum. I here aren protons in a moletle and if they ae equally coupled withthe electon, ten: How nity lines willbe observed ithe ESR spectram? How ac the lative intensities ofthese lines related to each othee? ‘Quantum mechanical expression of rotational energy levels is a = oe usual meanings. Show fat the above cing the appropriate quantum mechanical ion of energy. velsis given by the fact ‘Show thet the degeneracy of various roa +n, Molecular Spectroscopy $15 Explain, why many of the lotr rotational levels re thickly populated. ‘Show tht te rotational level whose quantum number is given by the expression figar) a yu YG) a tas mss popula, (©) Show that the rotational frequency is equal to (hisn"n JJ + 1). 4415 Esplin wy ony molecules having pemanet ipo momen: exibition spec (a) Ws ae th selection rules forthe 1 lets? (©) Describe the general appearance of amaeul ‘What information can be derived fom a otaonl spectra te following cassia expression forte fetencyofamonic ian of dione molecule ns of & diatomic mal spectrum of a diatomic whece the symbols have their usual meanings. (@) Show that the classical expression of potential energy of harmonic vibration ofa ditomic molecule is give by V= (2) bir. m7 where and ae the displacement 4 the wo atoms from their equilibrium ession of potential energy of a harmonic leis 417 (@ Quantum mecha Ve (04 D2) ‘where 0 is the vibrational quantum number. What are the permite values of v (0) Wht is zero-point energy’? Is it consistent with the uncertainty principle? (c) Explain, why only the lowest vibrational level is thickly populated, 3 for which dipole moment varies during al transitions of a diatomic solecule exeeating harmonic vibrations? (0) What is the general appearance of vib smolecule? (6) What information can be derived from vibrational spectrum? "> (@) The viteation of diatomic molecule is aakarmonic in nature, On ofthe potential enemy expressions in use i the Morse potential expression Ex Dall = expla (ig NP spectrum of a distonicuoppiqiy ae snopysuen roida-oriuis. Cs) ‘suojysoen tdin-or-ojéin pur vertus-ovsers_ (8) souooxsiony pew astosssogdeoud opetossp-axd put UoNEOSSI 2jdjanud uopuoy oR oynoqos 1 ssmosIG SCY oFH Ps so sotunea youd Supe Aq ona aD BoE TENN jo II aI AMS TY ‘yumnoods uowny wong 2H) pea gun amedinoo soy soug-n pe 2901S Jo somsua! a OP OH, (@) cepa e Meg woury 2 puny 2 1 yo wnneds unoads ueumry Puoreey azn oF saypig-pue pur SoyOIS_ JO ‘Seuss a op MOH JS soYoIg- TE PUP ry amp are eu (@) cau tose Jo saquann ane omy 8194 Eg Otay a4 te madde souyy uewey agp req) MoHs “2902H 0 toads enurey jeuormos and 991304 s24ns wonD2I>8 ap pod nots maze 99 1803 Su Yeu Jo Noe a1 EUR smug Jo 2ouaspa 430} ronenoe Soxmeysou RAE SSOP MOHL jane veuey 2 pooja 09 open Yenuoes an st yg GeMHoeds weUMY SIEGAL (2) CCP (0-0 aR20}0u ainaa}on, oWoreAlod, gum 2jnsqous oom ® Ye wms2ads wanes suogiseen | = 9205 esr ‘wont 9} poe “2 samen ancy me oy Cr D 4+ wae == av ia uansd 15 = 9) peg =, > 1,0 stomisuen ogy 39p Joquuonew =p re moys (P) eamoofout woqeossuoeaqa a1 305 31 WORDS yA () ‘Adoosonsods, voneioy-vonesaiA equine umuenb yuowesge 70 ‘azovano () "woauen eeeuepuy () Ka prszpan no op wpm “ue (P) lows sfaotaey Ub 20 Sq woNDeS a mF IA () ‘gun ure (SONG. fo angen Buseaouy spas Saseaap ATV SouNAIP oy He OWS sOH9y oT (a+ Det~av=av won 4a sarou omy 2 uae couDrpP fHa09 ‘an yep moyg “ueyu09 some BupuodsaLo0 op 5“ pu our 2p Jo Kotonbasy soueyaso wnaaqnbo Se uMOHy bi Adoosonsads ewe assay pops Jo yooqweaL ¥- IS518A Texbook of Physical. Chemistry ‘TRY YOURSELF PROBLEMS. NMR Spectra 41 Given below area fev PMR spectra. ‘The moleclar svete is given along with he spectrum. Weniy the various peaks {8e comesponding by ° cayciten, Molecular Spectroscopy: S19 ano,2uore Kdoasanzads YN. ue §HD00'HD s2]n22}0w ‘pune 2 ‘ont 584 ONHD Huo} 2 sons (sou porpe pam eaudn 209 toda nok op sou uondbosge sa Alsw AOH pp ‘or snp Jo umnsods ySet 2m PNPM roo os 7 So ‘3p yo sua ut produ smn yo woods YIyN 2414p 99 OOF € f ead ou soy NH ey 2g Sasy punodan ¥ Jo wrod pam HL cp a A leerca as ocs= are suesuoo 8 Sy. pote Vaspeusdtoc jo unde 2 As 219 [sw2d z1 sav] syed pt y4doxdos sen SLT poe 19 "ai syed uondios i i i i Fl i i : i i 3 i i 3 » Adoosonoads usa san ow: pus DP vo poy-no} 3224 219 SH*HDODHDN ‘unsoads uonnoras-(iy pasodxa si stp ose pUE aumonas amp snpaq ‘tpapoodsas pus Zo sop|suantannepss ye Sd ‘om sange> OH parodwo> amy jo umrveds YPAN BORNOSSE-Ko| UL, (0) [fjoanoodsar ‘oat ‘oH os 8 Ey so oto ‘jaqou GH 29} wnssads YAN am IAS “psu nba Jo Te "uneods WN ‘ay uy syed yousip amp sey IHU ipso. Ky “4 punodwo> arewose 24) Jo wanseds YIYN 2HeuIDyDS “prgpeps ype yoo poads am se au Se pay auo st pa aan ego a4, ‘Fea oma Jo stsvoo UBER YN "E9840 3 Ss ‘oye Tes Mdossauaads amram Aansouryy porstyd Jo 30092L VCRs522 A Textbook of Physical Chemistry Rotational Spectra Electronic Spectra 421 423 424 where = mo + me+ mg 5h between linear and linear molecules fom he (OF 3 700 : NHL 3500 : CH 3 000 : SHI 2 600: PH 2.400, "Bcplai the relative fequencies in terms of bond characteristics Figure 4.5.2 depict the plot of V versus Ax. What typeof graph do you expect between d¥7d(4) atl Ac? What sits slope? the stretching vibration frequency of hydrogen bonded O—H bond tify the following stateests (@) The vibrational sce oft electronic absorption spectrum is characteristic sonic Jevel whereas that of Muorescence spectrum is ‘Phosphorescence is intense from sod samples ‘The amount of phosphorescence depends onthe presence ofa heavy atom. the upp (© Less effective collisions in crossing. (2) Heavy atom singlet“osrplet transition chanoes of radiationess adiationless decay and decreases the chances of inteeystem crosing.} ‘The energy of n, x and n* orbitals of af-unsatuated carbonyl compounds ae lowered in a more polar solvent due to the solvation effects, The effec produced are (AB), > (Ee Predict, what effects on m > RY and speci ofthese compounds ar reco [Ans Blue shit (ravelength increases) for x ~n* transition} (A), 1 wanstons are produced if the foton Magnetic jesonanco Rotational Spectrum lbrational Spectrum Molecular Spectroscopy $23 NUMERICAL PROBLEMS He for hoon energy atthe radiofrequency of 17 field of one tesla, Calculate the nuclear g (b) The NMR signal ofa compound is found to be 240 Fz downfield from te TMS peak using a spectrometer operating at 60 MHZ, Calculate its chemical shift in ppm relative to TMS. [Ans. (2) 2310 6 () 4 ppm) (©) A paricular NOR instrument operates a 30256 MHz. Whit magnetic fields are requized to bring a hydrogen nucleus and 2 °C nucleus to resonance a this frequency. Given: g(F = 5584 and g("C) = 1.1404 (Ans. H; O710°T, °c; 28274 7) 792. Caleulate the energy levels late the NMR the relative population diference, Le. (ty ~ may +t) for id at 0.37 at 300 K (©) Repeat the problem 43a for protons. (6) The ESR spectrum of atomic hydogen was recorded on a spectrometer working at 9.302 GH. The vale of hyperfine cou ‘atomic hydrogen iP and 357.5 mi) in G and Mit? [Ans a, = 3 G or £40 Mit, a; = 1 G oF 2:80 Mite] 44 The septation between succesive lines ofthe rational spectrum ofa datoic 45 72 and, 3270 ct abso of eam ines a 1425 and 2 085 em and two weak absorptions at 1370 em! and 2800 em ‘Suggest assignment ofthese absorptions{28 or £si6 V1 w ynanou eyo ams pure ay Jo Kove Hoe AL, CY deinsaon sez yo sys pans> at Jo 68 ens}! Oa af 305 war or yeguoyod 2p UL ou OMT sox at YON sene9 os puro ayy 29, 3H 5M wot wonepes yo UTA WMEADHELS a4) SUA, OU PZ 60 8 ‘Wore paoxe mp jo uonmoxa Jo Alexa ay ams pox ao tp pu as ‘puna an mo; ato i SEO a1 WONEXD HY 8, JU FASE SKE 5 aqnopjous smc w 30 as auonRye punass yo ABsoHo HORS KL, 61 £4 L061 “S8V) sydoosonads 2451 ay “Sue TeATaU aM. Pe ‘ais oan tou ons 0 fA (wu g 860 Suv) Zip 30 Buoy pug 2p st eHAy Dd Z¢U60 Ma porERE>s sun soyong Jo setae © saoys fp, JO wnnaSds UEMEY HONEA 9, uy wort au onyiosge ous 1 Aouanbas eye. "uw ge BUENA hq ponos9 wy WH gop w sweadde sou wey 2M) JO 240 J “suonesqy Burpucdsa00 an pe acorn oi yo Aajuiad ayy vod woutI63 ov _ ons eaueped Buens 000g = ons ewe, pare, fenzeds uruey pus pore Suymoyoy mp sey FEY aq Y 066 a oy aan wea 70 poutod aU, )“UoLIaN0 aii sy = sod seo aU 9 HFIDD 24, sm 0a +200 = ay ame) +a © ‘a+ oH (pro ofuyo ABioue op sino I> 966 119d 49 £88 OH 4) st yg suo sp ons oe Ly Ausqucyy poqssyd fo yomreL ¥_ Yes526 A Textbook of Physical Chemisiry Vibratior-Rotation Spectrum, molecular levels is 6.507 48x 10° a, on. (Ans. 6.474 055 x {Ans, 4.906 x 423. Which ofthe viteaional modes of CO, ae IR active? Whats the line spacing inthe P and R branches ofthe vibetiontation spectrum ofthese vibrations ‘modes? (Ans, Aniymietic sich and ea ‘vibrations. Line spacing. ve raion evel are tna 4.24 Which of he vibestion odes of aceon ar IR active? What is he ne spacing in the P and braces ofthe vation rotation spectra of te hrasonl modes? (Ans. Anisyemetic stetch and one of the bending modes. Line spacing is 28 with intensity vaxiations inthe ratio of 3:1 due to hydrogen sams J @ ANNEXURE ‘System AX A Qualitative Study of Quantum Mechanical Treatment of Spin Transitions in AX, A, and AX; Systems axe described below. Sie eon veo sucka (m= 12 id ad = 1 designated as spin) there are le magnetic states that correspond ote fou possible combinations of espn quanti aumbcrs of A and X protons. These are shown in Table A.1 Table A. Nuclear Spin Wave Functions for AX System mie mi) m0) ef? ; e 1 va = acavatsy a ; 0 = KAYAK) + $ a i= Hayao, ++ -t 1 5 = BAN * Subsea af wave function rand B represen spin wa ‘The energies of the states shown in Table A.L can be evaluated as sual by cexaploying the expression _ Villy an in the AX system do not interact with each other, then the pl the sum of energy operators for the individ protons, Hg = Heg(A) + Hg) It-can be shown that with the form of wave functions given in Table A.1, the nergy of a system is simply the sum of individual energies of protons.x Gogivig= "4 x oy 4orH o comwvig =" (o-na "ADA yv civ = TL nove tal -tio-patis zon a funy Kaa womnswo4y word egg ov iad dese ea Recs XY WaIeAS 04110} suontsueHL Uids PaMOIY ev aay epoanl e weishs xv 20} suonoung aney jo so}B10ua zy IgE, TV 2198] Hf wonY@ am pu postop 2q 24ge fy Vans suonouny ones a Jo sorious om (eV) pure (2) sha SuRoHO “Fig ut uous aqu%ap axe soBuey> A@iaus pawsosse ayy pur s ane oso, CV a1aRL WL ues unds Powe OU, x . ew) a {so -v sb} 9% 3 Zl py . » {eon 24e-} 0 cw fow-v%s2 | -n%y ‘8 ong aq wo sms wood any vonenbo ups OM ea et Tw axay g (22) | J ca a (22) uit = twas af E | ae a") costye=" 5 powsidt 5 uonnuy ext us vrai 8 *7 300 A " ‘wns mr wotodo? 29 panda. somo 2917 a * oogevn- PY Seu we wo oo ! srezado umn guey 2:, ¥ 7 oes apoudemu tpn wore stoma} ene Sap oS a ie cooing = Vato) dla = My wd fe : 4 san pag node eta po sonsend ay atojo 8 wt wore wasp yo Khoo Teed ou, we — (cv) ad (30 1001 GOD) + {Ov} KV)" En Cv}0) = ‘amy ah “as feooRoso ue ayapsue> suopouny mds ay Sous spfona Jeno 930} 9 = wy omsuen uids ZoyB:opun srajnu ap 309 1 = wy es L so1ms onodeut no} Jo sofsous Jo 0p annepa ap Sesnewioys SAEs eT'Y amy Ya>taota> a a syfous yo 3920 aanmas on %o we yews 99 01 Yo Zomssy ‘smoyjoys8 are sonmeypou uinyuenb wo postop se sa uo 61S dossousads somo2jopy aasnuryg,gorstyd Jo yoo] ¥ ges530A Texbook of Physical Chemistry The System A, ‘Thus, two transitions atthe indicated energy changes are observed as shown at the foot of Fig. A-la The chemical shift between the wo is 7 Wox- 04) wo UE the spins of protons A and X itract with each othe, iis expected thatthe system of pra oppose spins wave actos and) (ie, of wave functions yo tnd ofthe two lines of either A proton or X proton willbe bal ofthe parent lie observed in the absence of spin-spin interactions. Ver= att}a2) 3. Total mognetic quantum number equal o zero a this tate, one nucleus ce the two nile are indstinguishable, combinations of spin wavefunctions ‘Symmetric wave function: et + Buyat Yias™ Fy [aA + BLVAEH Antisymmetric wave function: Ware [2€1)B2) - 10023) ind stand for the symmetic and antsyrmmetic nature of Molecular Spectroscopy 31 Quantum mechanically, the spin transitions are allowed only amongst ether symmetric or antisymmetic wave functions. Te spin transitions ftom symmetric tw antisymmetric wave functions or vice versa are forbidden. Besides the above restriction, the selection rule permits only those transitions for which Am, = = 1 He Vor and Wy 4! The energy diagram shown in is modified to the one shown in Fig. A2b. Since the transitions only amongst symmetric wave functions are allowed, i is ‘obvious fiom Fig, A2b thatthe energies of allowed transitions 4, Yo, and as those observed in the absence of spin-spin, ance line observed in the absence of spin-spin ‘Thus, we conclude that the chemical equivalent protons do not show spin-spin spliting inspite of the fact that they do involve spin-spin interactions. For the system AX;, we have e tates as deseribed in Table A.4, Let {and ob the silng constants or rotons Aad Xespecel, let we write Lh &yotAa-ope (AS) Elm as Fer the ty soil bely= WD. 0 ant dus B= ~ Gi) Wa} = -suoppesaormnds am wosououg TVA ba yo su fo aovasge otp my agnaajoas §Xy 20) wreserp BIN et (gz Ya) Maa. a “aun % px sve £9 ap a senoypuodiad sove pojowa aonm ‘sme’: $09 Sa ‘sumyd > pus si £5 a 1 seqnxpuadad soe pow oma sme t2yD—TH Sa ‘ous Ywop94 w pue sr "9 1 (gy Bu0pe Kou Jo sp “5 ae ona on sour roan sede yon soesed sxe 9 aH, (O° 5B) Sug stax “das eg stnoour SN w sud yaps8e sy pu eS STS HL “smouey seam doos8 sup 0 sordurey ‘aud repos pavers » pu sxe" a 0h aye ni sxe pIojoaN ‘rigs Buoqe #9 punts Jo spre we Suyany soxeojou soptyut dioi# Wied SL Wg dnow ywlod ume sdoos8 fq Jo dura ‘spe *2 om oy sou We pron dros od sm, “g dnovp quIod Je woredosu09 2yor spre pogo ps ‘vonoager paseo} 0a Sq uoreS sxe "Ze yo uaproutoo sixe ue Hom somo axp Jo amuao ein nox sessed pur swore Hoy Jo 240 pv wore Nsopou su wns, soe an ap g dooss od agp 3 ae ny pestis Shs suoweayday sy puo Kuouauky sopro2qoyy Guasnaryg porssyd fo yoowney V yes546. ‘A Textbook of Physical Chemistry Fig. 528 An example of the point group Day Point Group 0.4, Point Group T, Point Group 0}, The point group T, includes are easily visualised by drawing a tetrahed cube (Fig. 5.2.9). ‘A tetrahedron has the following symmetry elements ‘© our C, axes of cotaton; each passing through two opposite apices ofthe cube (Ge. one apex and the centre of the opposite fae ofthe tetrahedson), Each of these axes generates C, end C} operations—a total of eight operations * Three 5, through the centres ofan opposite pis offices ofthe cube. Each ofthese generates te operations Sy, 52 (= Cand sof rotation; each pas 1 through the centres ofan opposite pais axes generates an operation C; which are already included in S, operations. © Six o4 planes of syrumet Tine joining the other ‘Thus, we have the following to vertices and biseeting the 2 generate sx operations symmetry operations in the point group Ty E,8Cy,3C,, 684,60, These are 24 in nue The point group O, includes symmetry elements possessed by an octahedron, ‘These are easily visualised by drawing an octahedron within a cube (Fig. 5.210). Fig. 5.29 tetrahedron drawn wighin a cube Molecular Symmetry and ls Applications S47 foucrs o J os Fig. 52.10 Am octahetron drawn within a cube ‘An getahadton has the following symmetry elements 1 Three 5, axes of rotation; each passing through opposite apices. Each generates the operat (= Cy) and S}-—a total of six operations excluting the ‘operations C; Three C; axes of rotation coinciding ach generates C; and CP oper 5 the operation of inversion. This is also perations. cach passing through four ofthe six spices each passing through two apices and bisecting two ofthese generates an operat generated by each of # Three horizontal planes © Six vertical planes ‘opposite edge Thus, we have the f EC, ‘These are 48 in number ‘Thisis highy syrametical group with h= 120, These ae 6, 12C,12C3, 206, 15C 1, 125;q 125;p 205, and odecabedeon and Buckminster ulerence (Cy) 65.36 CB) 5, 65 85 30 6%soak +g use = 4 M2 £ pus £49 soox=tr yea x ‘so0aHt gs00k=% pue gusé=tx —s924 pauoduoo-e pusr—=' pur gsoox='x worm mouoduorx ‘smoyloj se a8 S194 pormos amp Jo savodo>< pur -r au, 9 ove ue 69 a0 Jo sono ayn Buuapisvoo Aq pantop ay Sew ( wuawun uoneiedo a woxy Funzes) wnoWs J9pIO 2p no Buydaze Aq sda sno payom 0g we> suo} met tasw Sons dsp crete Se (6 °C) eho 7 Us sapsep spins oy shepxse'pwnenpsa som ye lo souaq quod 2 0 mguEdoo £24 soBuey> ‘0% e241, uoymado%o ‘souaH wd Jo mowodunoo « ow saBuey> 081 &q soeex moge won oy, uomosedo Fy (6 -@) wonesedo gam poBueypun wusor mod & Jo sowuIpI0eD ay], uopmuado $59 suonvonddy sy pur Knoumeks sopm2}oyy wig ‘9 amd wonsepar oq, * 30 pus °o “9 “yam Joe ut swattaye AnoxmKs ou, “0 doos® wd) sajoaqou SN pur dnos8 wed) FH yo sayduexs a Bupye Aq pens: Buroq st sy “(END may) x (weno einfon) st doneondinnur Jo spo ou, ‘Nos WAS 2m BuOqE pu wnjoo uani8 29 open watoys st onpoud a, uonRsad AneMTEGS Be 20pERY IE uunjoo qoeo pe mor ypeg “2feaajou v Jo suonezodo Anounés Jo soqumi aq) se ‘saunoo par sos Sues sesopeyour a} ay, "age) woneadayau: Gow? ¥ Jo m9} Ur uno4s are dooif iwjod e Jo suonesodo nouns yo sionposd Areug ou, “dno ru yo suonexado Jo age) oq “dn023 30 04 ‘Gnas © au aymoajou ye 4 wopeo140 13339 "29 dno1 wiod ‘24204 Saou NL wonewio)sued, ‘suoneiado ‘Ayounhs so 6uns}su09 dnoip wed STINOTION V NO SNOLLVHSdO AWLAWIWAS 40 ONLISISNOO dNOHD ss ‘AV st -wonmysp &q yar “q Jo wooxdoas ap st. HN SSW SH, yeaa 2° (say 2m) a= \.V¥ 2 vid = |.¥@v) 7 @= a9 20) Yad = |.vaV 20 Vi = |.¥G 08 Wiad = |.¥8 av 128 9m *.¥,.4 &4S99IS oN wo woREDNdeTRE BR a-v om 2p osouax 24 uy syeooxda1 2 Jo woneutguios 9 01 yenb> 4 ax8 » yo swoaje(esou 30) om Jo uoremgaio w Jo yeondos an TE OUS (LY Suan 6 jojssadio ange amp wx (ROOK AL, T= VAC= XV sen yons x sty Jo eoxdsa1 a “uoMUYDP Kg "dor oun yo wowoja ue ose st yor ‘Teoouds3a» sey dos v Jo saquaun £194 vonnios, b's wordod swwowrarg 40 yeo0id)90 Ansmioyy popsyg fo yoowrAL VTS554 A Textbook of Physical Chemistry ‘Comments on Table 5.5.1 Transformation Matrices for the Paint Group Ca, © CUBS T) > 6 HI LHL OGLE Hh) this, 650, 04 (216.09) Using the matrix notations, we have © oC, Fi: Ha) > 04th: Ha) Bhs Hy) = oH) tats, 0% C3= 6, Using te mnicsonion verve (5 9)( 8) =(3 8) aed + C9 Hy Hg) Cs Hy) TH HS) = 0 UH: Hg) that vier temas vere (5 °)( 2)e(3 9) Crpsetic arcs fF: Hy) = o4fF Ha) thats, G.9,=0% + 0% (HH) > Gr Goi =, ; (1 oy oy_p1 0 Using te mtx ovations wetave (5 $)( t)=( « Gow Hi) Wy HS CANS HA) thai Using te ocicsontins wete (3 °)(5 9}=(S 2) Crd Gq © 05 (Hy; Hy) > oF: Hy) > Uy: HJ = CIA, Hy) thats, 00,2 C; fo 4) C 4) aorRC Using the matrix notaons, we have ‘The following points from Table 55.1 may be highlight + Bach row and each column includes each symmetry operation once and only once. ‘Each row and each c sn i earange list ofthe symmety operations «No two ow (oro columns) are identical The symmetry clements in ammonia ae E, C3. ox comespondingsymmety operations ate B,C, C3, 6 6,(2) end 0,(3). The x(2) and 0, Figure 5.5.2 displays an ammonia molecule along with the Cartesian axes. Molecular Symmetry and Its Applications 555 Fig-582 Ammonis molecule within cube The mates forthe operations E, Cy C3, 6), (2) and 62) canbe shown in he flowing pas Operation E The operation E does not change the coordinate of a point. Hence aaa 0 mew Bld Sodas Operation Cy ‘The C, axis of rotation i sown in Fig. 55.3. ‘The oation by 2a sou the C; axis trows H, 10 Hy yo Hy and H, 10H, This rotation also sends te exis x mz, imo x and int y. Thus the coordinates of 2 put 24, those of 1) afer rotation change acordng othe following scheme Yay, yazan Z=x In matrix notation, this change is expeessed as Fig 553 C, ms of ce .2 rotation n Ni 7 Operation C3 This rotation sods HoH, Hy fo H, and HoH. This oation als sends the ans it , yin 2a into Tus, the coordinates ofa point (say those of Hater rotation change acocding to the following scheme vee yer and vay‘soy Sospuodso00 2 29 eu synsan ay, Ao uomezedo axouoe8 J 5 oo 9 (oot) (00 orelerog (oo lor PH SHH) @'2sCHSHSH OCH a swoendo ay purge ae swonsod ron 3 pUe 1 “H Avo pnt San ee tae ur szebs un uous 204 suOnEUEGCD 23ND TOM OH NA we @e ayo care saouneus Butpoodsanno 2p yo oma das £30 (yo an ato Aq 900 enpsoocH 3 Suess) unoys 29pu0 2p UE pur ‘poSueyoun 1 sane vortado Axggop! Wem ip () se Kew-aUitens uonum aq ue axenbs 24) DUL-Z5 age UE mous st dnoaS yorod ap 20} ayge wos yuiquoo doo UL gg suojnonday sip pun raunuss spor se possandyo st Banyo sip ‘uoniou Xue gp faz pu raf xox "mopp9 wans8 auagas 01 Bumpiooce ofuey> aoqDaye9 Jaye ‘pus cw steep pase $8 (20 yBnoay uoRsey a ays Sur m onogs a (¢7'o sunduonsapa) au, (9 woumsndo os Bonoata SUL “Hon °H par *H o1aE Ate ol been Saas (itp snap ‘ts apd eo spunea omy 2 pe? on S30 3p see Sonne hra ue gob wrote a “aps's By uy unoys 91 (2)'0 sum uoneayas ay, (@)'0 woumuadg, (est) \xho 1 0) } ss psn spa rez pm xa Kaz “auoyos Suproroy 2p 01 Fumpuoooe =Boey> uopsayas Jaye Aaaspuay porsiyd fo yoomraL ¥ 986588 A Textbook of Physical Chemistry Characteristics of Point Group HI>G OHH) 0 tables of H,0 and NH deseribed in Table 5.5.1 and 5.52, respectively + One element in the group must commute with all wth members and leave them unchanged. ‘This property is also satisfied by the ide tion ofa group. also an element ofthe group. «point group Cy. The plane cation holds good. This maybe exemplified by the combination Co, (1) o,() ofthe pint group C, Loo, roo G+) foo We ° «|p 0 ill=fo 0 if 2 o| loon lon 1 o)y(t-0 0) ft oo 1|=jo loro) to = (Go(D)o,2)=E ‘This may be extended 10 any numberof combi ‘Molecular Symmetry and Its Applications 559 58 CLASSES OF SYMMETRY OPERATIONS ‘The element of a group can be separated into smaller sets, known as clases. This is based on the similarity transformation defined as B=X'AK where A, Band X are the elements ofthe oup. This expression the si Teach clemera of a gr0Up js subjected tn similarity tansformation by each element of the group, thea the 1 group and one of ‘example, 2 and 5 elements ‘We workout the classes in the point group listed above. Similarity Transformation of E We have ele =F EE GAYE O42) = 02902) =E QBN 6.3) = 6 30,3) =E Since Eis similarity transform to sel, the element E belongs to a cass ofthe Ero. Transformation of C} we have = 2.0) = 6)0(2)= ¢ ‘The similarity transformation of ‘or C}. Thus, the operations Cj and C} belong to one class of aec} 6,02) = 3 2)0,83) = ity wansformation of CP always give C} or C2ale ou wo Git I- ites I+ ale ow oe ot STs SS aS sro egy « sseige ‘unoys SonsuaIoenys Ma} y —_JOSORSHO}OBIEY fe $630) £5 pow $9 sures euonNos ana oj poo spoy = upaodsanco om sue ,0 a¥p uo swiod [fe samp doos? ayy ut ‘Anoans »poptscad ssp Sues 2tp 01 $00,290 puto suoqRodo wo p may) ‘pur $5 suoneiedo uoneior aul + sentesuamy Aq sanyo © ut yore axe "D pur #7 suoneiodo Cnounuks ayy, « dnc g

6 uxg 9009 us=*P 6 s009 9009 us =" seuano 2049 Jo suojped ryndue ap ayn am Os wana 0 sgt patp BuuKopISUED, somo} 9 ar sjrigr0 4 wo poseg * dnas8 yuod ayy yo (1 x 1 st you) saoeeu von €Ls suonmnddy sy po Krowuks sr22}094 rei 'Puo yo0H reUao *puo wena rego. P uo yeh, oye uy 86x0 po sero“ pue “wo suoneaodo Sapounus jo AYA STS BL Mie) 40) 4 “009 "809 reuso "duo yoo rai ‘duo yan reuao ‘oqoy se ae sergio“ uo oY UL duo ona Aasquoyy ooyshug fo yooqreas ¥ TLS(omm00.) 9rrs Ba seoinen, Uoewuojsues, ‘smoylay se au spiguo wo paseg "2 dos od a Jo (1 | ao ype) someW uoneunoysuEN 2a, ; f "os Caspar jo2tsiyd Jo yoowrsy ¥ HLS SS suowoonday 54 pun Cinuau’s sop2290pycarer ee g aeh (6 usd ome ifja as = (6 ms 9 us)" = (4) Ko 426 usg us= (6 msg us) "Mo =( 2) 6 us (HE = ds 3f) 9 us = 6 us9 usif = a) ? 6 weg ump =H a=coa euqio“d uo siraya 929 emeL ‘9 21481 UF wnoys ame penquo “A wo S194 OU, 18th [ome E-a soZf) ome ote 68% 14 Eh [os 5-6 soo h-| g ups =(6 ws 9 us)"%0= (4d) "0 eaai (+ end a] (Sus 9 ws) *0=(‘A) ‘ ‘ayo “dad.us aus =(6us 9 us) taka Zh. z zh wo wy ioe(‘ae Eouth[om Ea sotl) oa tome mip=C09 g abuth. rg [+e $9 ff }our-Couro ano ‘SUS NRL UF WaOYS a NGO “A vO SOON aU, 6 ap 2 wo [fs — gp) Zh ss om Sa us [f+ s00 © =16 — opps00 # £8 0 nopoindg “9 4 we © 6 500 2= @ + 09) 9-46 ~ ooCDU reg 6 ms © ~6 s09 © 2 (6 + 9) s00 =(6 — .904)800 Ey 1 oysivdg “Wo, US suoneandy sy pun Kuowuls spomOH cd {duo 0K reo “duo weya base ~ br00== (= 081)909 oped “5 6s ©3002 <8 9) ws Lone Oa 6 [hg so E w(6 ~ 9) 09-=Lore~ 609 ¥ 1 woyasadg {9 up £9 mo Ff a6 +sny an atont-Oue 6 owedg © yeu Eh + amo E_ = eras soet ~ 8:09 ‘smoyoy se 70d ws pur d s0> uo 4 = 209 21d ~ acy 01 saueys d ‘ep 6 oe 21 - a z No S-sgiarsedimpd — “Xp =%D ‘oueyo Buraonoy ya ous ot surewar g aySuP uonsaqjax Sung, sy so08sepun 6 2ffue 2 HN puog am 1 suopmiado wowDg/e 1°§ Sy) oueyd2e “ove 4 or soBory> & “$5 20y pe ozI A oy SoBUEND A 5 soy “SOM sorjdde uoneos an seu Jo 29quima 2, Sw ‘sxe wore Jo s9p30 amp sty aN "U,09E x uO 04 BUEYD d ursuos surewr g ua po. ap WL oprouteo sr voNNON ap. Moniedo woo “d pie g uo megs ON uoypiodo Gyuopy od peg afs0e wo saya Buynoroy amp ane aa 5 doosd aud emp o suomezodo soe sy 304 ‘wrest ‘upg us=4 9 soo us=" 9900-74 anny 2% ‘uonm Jo syegHo d aw Buoprsu0) us pue 6 800 uo 93 ou SN yo wope1@BO ures a 6 pueg uo oya (a1NOsTON VINOMWY) ST¥LIaHO 4 40 STaNVXa "9 dNOUD LNIOd Aasrunyg pooisya fo yoounay ¥ 915518 A Textbook of Physical Chemistry Effect on p, Since poi does aot involve angle, we will have Orbital Transformation The tratsormation matrices based on p Matrices follows. &y @ on 1 1 ae 2-2] (7° Bal lon 7) EXAMPLE OF d ORBITALS (PHOSPHORUS TRICHLORIDE) CConsideing the 34 orbitals of phosphors, we have Bsn 29 dy = 308? 2-1 4,2 in 80s Bcos 9 i: pin? 8.08 29 Ge=sin B08 Osin @ Effect on cos 29 The effet on cos 2¢ and sin 2p ar a and sin 2g Cy Operation 1 cos 219 120") =~ cs (60-29) =~ 4 cos sin 2p- 127) = cos 60-29) =~ 4 cor 29-3 sin29 . ff sia 2¢p~ 1209 = sin 60"-29)= J cos 29- + sin 2 G Operation a eee Sn 49-247) = sin "299-8 0s 29-3 sin 29 my, Operation ! ~ 29) = cos 29 180° - 9) =—sin 29 Molecular Symmetry and Its Applications 579 1mm, Operation 5 cos 6r"=-29)=- + cos 29- fF sin 29 008 2000 ~ 9) =: 3 8 santa 9) x-sn("-29 =— fee 29 snap ‘rm, Operation t B £06 160° — 9) =— 00s (60° -29)= 5.60829 + | i029 B 1 sin 2067 - «) «sin or" -29)= {Boon 29+ sin29 With these, the effect on d o Since d_, orbital does not involve angle g, we will have Elds)= 4, Ov,(4) = 2 2 Theelfects on d,s» orbital are shown in Table 5.7. = E(sin? 6 cos 29) = sin? 000s 29= ds» cin? zo(-2 )=-$ ~ 2 cpat vexig =i o(-Lenag- flame) =—Lay.g By A Log spares a) + fee * 8 cos 29) = sin? cos 29 ds» : a 5 1 fi aevap esto Lente Bante) = fpf si 0-29 + Fan2g) = —Mdyy + Pa cos 29) = sie of-jen2e+ ff 29) = ~F4e-y + ptsjqionpas jo swum wy UoNRaESSES stom JapSUO =A ‘yo suonezedo Anaumts jo suoneuasaxds yo s05eq m9} Soquosep 1'¢ YOnD9S SNOLWINASSUdaY F7TSIONGaUUI ANY JTeIONGaY e's IS iGanis THe fos att es 567 seoineyi sod op 0} sug PUD paregssomNEU YONeULOISHEA aq, —_YONBUO}SUEA, =(-98 ox 4f) oo wr=tomo moana acme § (dus! — asco 2h) gsoa quis = @urs9 soo gus)" =p) Wo = (oot sso $f.) gooon= oanosorgan 2 =) Mp=d ug 29 ws= (6 sg s0o9 us) ™0 = (°P)"ND “o-vrits (oms§- nq {fom w-@ wo momio= C9 =(0us$-osm foro ure (6 ws9 09 us} = PFD Mp ad us song uys=(6 use 9099 UN) = CPT eye uo swona obs ome. ee, UNO Ors ay w unoys ap 20 say a4 ‘puo ola 186 swopwonday 91 puo Kasounuks smecnoyy “pa mp2 = (say "f « 65002) osooous = soo 9s029u05)'o = CHINO vfs o=(ouny hee ie 918 = (400 9800 gu) "MD = Pp) ts iG oni} oof) q i %p—=d s009 song us = (6 5009 5009 Us) No = ("pO - (conj}-sm¥Jpwomasmesmomnp =e =(om$f-rsso! Jomo mee m9 m0 mono pad uisg s009 us =(6 us9 soo uly = MDa eyo p uo swoya 61's c1ae, reo 6S aR w UMOUS ATE %p Uo Soy BM, *p uo aya Eh = exan? sacses2bs) m= ae onnan Mo =C9%0 pba dept a (scan! + 6500 2h-)9 sa (62 us0 29/0 = ope neh (ecws§ 4 hee 6c 59 ,08) "49 =( 4p —edcusg sas = (Oz ws gu8)"™0 =)" opty rife = (s20n$ ses eh pap=@eme w= “nk [om somo an oom ano x9 “p= dzusg qus= (oc us 9 wusda = Cle revaio “pu siona a's eine. . jeusuo S15 gE UY Uac a %p Uo NIOND mu, p uo wo43 Aasspuoyy pow fo Y0OQH2L ¥ OBS582 A Textbook of Physical Chemistry iiarity transformation X!AX where the max pro Xe (& “Ns -ysr ir 1 where = a and y= Ji. The matix Xie the inverse of matrix X (by definition, XX“! = £) and is given by [* x2 ap) 0 Six xh | ly x a) Thos foo 1y(-2Bx 0 By) fuse Yue aay axe}1o ol] yse 3x -ysy|=|-a8r 0 yy toto) lyse yy3x psy) ease thx py, sexan=|0 ix | asx 0 “5 by yy Jase ax psy, ip ih o =|82 a2 0 oo 1 ‘We find that the matrix A (which involves zeros along the diagonal and at the other places distributed unsymmerc S (ohich involves zeros distbuted symm the nonzero elements inthe matrix S ae blocks of the order 2 x 2 and 1% 1, eos now the above similarity transfor Xx" is extended tothe coresponding (ofthe point group C,,, we get o10) f- dp o 7 rererfi otfr=|-v3 -y2 0 -(¥, AA and nal) i transformed into the matrix too} (o o 1) 8h 100) p10 ware roo ileelo = of foro} loo 01) [- “G0 ofr=| 8h 2 0 (¥, BP) a o} ("oo 1) (ae ‘Theorem 1 Molecular Symmetry and is Applications $83 010) (-4n ih 3) oo xtoorerfiook=|62 mz olx(22 3 ) ad) x oke[te ole(Ge that each ofthe original matrix representation is changed into a matix ‘nonzero elements along the diggonal and each one is factored into two situated 252 and 1x1 Blocks, respectively, We also find tha the rest matrices ae identical to the mati represetatons based on the translation and T,, respectively. Thus, the abov to changing the basis of representation from bond “The ireducible representations play fundamental roe inthe application of symmetry to molecular problems. 9 CHARACTERS OF MATRICES ) ofa square matix of dimension n isthe sum 69.1) s conveyed by the transformation matrices of any the character of these matrices. There are two theorems concerning the behaviour of characters. These are as fallows If C= AB and D = BA, then the characters of C and D are identical By definition, coursverof C= 356, = 35 ) (oduct of two marbers is commutative) te) (Onder of sion is ese) dy = Characier of D (592)(a 22) (oe BE) (5 9) Ge ‘gy Suuosoudony enews ay jo My rwsUs|9 dol » wt suopsodo snore yo uoneunts om suasoidasy UoHLBWINS aH, ( 0 a "2 b sr 4z poe“) sonon jruonesten ‘a wo posng * dou? quod axp Jo wowyesasendas ofan ‘roe st vortewosexdas ayqonpant owes an on BusFuojaq suonesedo Axum snows ayy Jo s2u7EH 0 ‘Swuauofe iezaztp Zuypuodseno> ow Jo sonpoxd ay yo wens ayp ye seme SH, se ua 99 Aor (91'S) bs nord e jo (e2ouvem Buxpuodsauoo an yo J9p10 2H Sroanoadsax yonya} swonewosaids yy pe yy 9430 SUOSUoLND 2p a "0 poe saseo om JO SINREIE AL + cay net TE am ‘quae euoBeIps1 Jo yee u + sey woneredoAauaps or Buypueds=3109 ‘Tavera oui Uo}SuSU jo Uoreyuosasda) a0 900 AO Wi Yor SI AML & 1 oe ae ‘anu pn om seme aus om Sey SEIS oy sumo amet ge sus "aE = = ABE death az 04) -erteoguo et you Jo o00 oxo svonmt2sn 99 ORY 0) SUPICO = fap woqn ps0 ne 21] 20 1+ 01 fenbo smn 29 a8 onenoseidas 2[gronpous 240 Aue wt suonenosaidas Jo ss2)oee49 24) ‘2000 ews ea ny amp sores amy « ag soms € 0mm + 9H gh K EH GLX TH gL = MCOIRE + COLNE + fa) wn Hows pvo|suaunp-200 B55 dhor8 mod o1p 40 suonewasados ajqonpan sno} in Jo ype ‘St eM ‘oy suopudo Anoumnts x8 40 yowe 0p sroeneg au $e | +2404 TP SuoMERESaideN 2[q!NPAUT aM JO 24D x4 "29 drow qwyod M1 Jo suonewuasexdey 0% “ ‘Kyoumu ‘suonerado Anaunks snog sepnjoat "9 dnosd 29 3f (opes98UN to) car||o ‘gus popuodde sia “1+ st uonexodo wossa4ut Jo oteanyo an (ape tHe calle 3, wiv popuadde \duosqns an “Sngunafs Jo a0 8 Cw|]o cw {lo ca |]o cw] Lo (or = 2 (ox =(0v4 STOGMAS NaNITINN 40 NoUdIuOS3a_ SI's somos ajgionpour ureyoo fo soF0q ayy UNO} YOY 2 pu & Jo suouquioo Areug ax noge UoREUUOGLT sapinondaoR|d SHY, LA WORDAS A wonoag AT wonD9s wowsoue amp Bu ‘wom, ae -doo:8 aod an yo suoyezale AnounKs ass op is aoe SLL, YL MONeG yesn st yorys voneosaxdas agtonpas wezodus ue J9pIsues mam UONDOS Sip ‘dno wud 249 Jo joquiss saryUgHag 2m si 20eId SHH, 1 MoR>—g (@3LISIASE—SNOLLNAS3Ud3Y 37810NGaUE! OLNI NOLLNTOSSY sea Ja SLI GNY SUOLOIA TYNOUWISNVUL NO G3SVa NOLVANaS3udIY 318IONGIy suon9es a ay ‘woman axe Teuonexgts ue quOH29[9 pe “sTeNRHO zyNoofoR sapORE ruuou jo mnoranyoq Anaunuks axp masaaday 0 posn ase sjoquiss anoge 24 Ree nee ‘ojo jesouo8 oy, dnos® x jo suormmuasanday aalonpaus essa} RAEN Y swore noge uo wnivowoul rya3ue Jo “Ipanrads— "one 21 porn sfoqUlle 3 sdnoxd eau ap 20} pase Aretsa st woneOU =U y+ 11 0s pu 1 Aq uorsuotip-ontg ‘Aq revorsuowp-ot 8 soo uonmosoudas rouoisuaunp-oyfiy Jo woRRURISICL « £65 suonwonday 511 peo Kruauss smmo2}0y) Aastuoyy Wwo1shye 0 AOOWOY 6Smmetry and Its Applications 5 584. A Teubook of Physical Chemisiry Molecalar Symmetry and Appi is ‘The character of the a wwe have ted of writing expl mine its character bythe following observations * fan atom and its associated vectors are shifted (0 diferent postion sue by any symmetry operation, then the corresponding diagonal positions ony zeros and thus tee consbutions towards the character of the ansfornation matrix is zero, ‘+ fan stom remains unsifted in asymmetry operation, the comresponding disgonsd . position include nonzeros and their contributions towards te character ofthe T 2 transformation matrix is nonzero, ) (rwce) (ei (com one 1(1¢ 2605 120) =0° 26 Thus, he working procedur «an operation (one in eack cl atoms and determine the core _iven below, expression (6 5.133) whe For 1,0 (point group Cy), we have caer ‘Mentty Operation atoms and also thet vectors remain unshifed. Fo each atom, there will be +1 for each of the three vectors along the diagonal ofthe Irreducible Representations Js -1 foreach vector and a total of -3f Reflection Operation The effect of te vector perpendicular to the reflectir remain unaltered. Hence the conti #0. Rotation Operation The effect of clockwise rotation about the z-axis by an angle Bis expressed as Hee) (6.16. Hence, the contribution towacds character of an unshifted atom is 1 +2 cos @ sede oe Representations of rae eer Improper Rotation The effect of clockwise rotation about the z-axis followed by naar Irreducible presenta reflection in plane perpeadiy Cee 2 Hence, the contibution towards character of an unsifted atom is ~ 1 +2 cos 8. ‘With te above gui ines, we an tabulate the reducible representation ofa group.curs, PRs iy {gy 20pt0 Jo deo = 30 (fy wolsuounp 30) vonenesoxdayefqionpout wy 220} ‘mq 8 uno; omy * 16 suonauny jos yeuouoypo ue aney am asodng {y Uoneiedo Knounks ay) 10 s0wdo ays} PUP “uopemasaidas 2jq}np ‘aya woperado yy amp 03 Supuasoxdos xu 24) Jo SIPEIEYD tp “doos3 a Jo J9ps0 au st seomme jo wosustaip amp st '7 219% yours pa¥ “uomemasexdan 2jqronpant wa pouy ‘iresado uonsofoud oun Burs ing St opnoooR ® JO .7TVS AHL, ‘O/YS :voreasqqe) voneumquaon rau paxdepe ‘ip seaqoaur suaygoud sejncajout Ayduns 0 Kaoayy Unor8 30 won WOLVEAdO NOLOSPOUd BML LES tay eve tac 8vp= "1 20H ‘uopeyuassades a]qnonpoy aang 20 oqnaqour sop 204 3 dos8 vod 991 584091 6S Suomnon dy sp pw Carouauts comnoeyopy SeSgEN Jo ammonns au, ‘uoneuasads o|qronpaut ur wi 2ijosa puE Wore YEO Wo SOWA youea soma 30509 ou) wo EW o voRNAEeN 2]EFONPE 2H 1803} tg STDs ae ve My Som ‘2jqe) soezey> aun wou} suonenmasozdan apqhonp223p £ Tris 0 ee (nee se |(cles) [ Se |cnle P09 "9 *E wopmuasauday 4p poy, ney 28“, dooH# HOA) 20g saopnyosend) ofqznpoll NU paajosss PU MRE YoRO UO ‘soma juonysuen sam 2A uo pose aUEYoU 0 wRSSedadaatnpal a 0 POH, 31's) SHES My sen Uuonnjog zorsweqoid Uuopnjes Fors werqoud daasruoig patsyd fo 70081 ¥ 96S598 A Textbook of Physical Chemistry tye ow folecular Symmetry and les Applications samt operation B on one of theft istration of Eq. (6.17.6) Since the function 4" ’s are independent ofthe operation, we can cence the ight ofthe above expression as ‘The effects of symmetry operations on x, y and 2 ae as follows. = a ~ aye : (0 canying ou the summation ove only the term fr which =f’ survives. Hence, 12} + (Sb, 2 wee : : $E,[n@ 173) ax (Fy : * (uae + (ly : Defining the projection operator as In the present case, 6, = and 4 = y = 4S In (6.174) In Bg, (5.17.6) if s’ = 1 and ¢’ = 1, we wilh gor ‘ BE g=6 ie Byres eee eee ‘This may be verified from the following explicit expressions. ans) ; BP y= | Tr je ae [FE rend on) = eran Bor For example, te C, operation ofthe pont group Cy, oF the coordinates x= #), fe ashen 20 9) opened os, ~y2 ~Y3/2. 0) i] lz -y2 ally! 0.0 In Ba (517, = I then which in the presen ex becomes fret By soy ic da- Pv + 01@‘woperuasaxdasagtonpaust uoaid v o) mnqmnven 20H Soop Yep waUY> aM SHE|UUE YONDURY w Op ‘uay soyeado vonoaford amp wp snorago nf oF anoge 2X9 Oy yosoudas Jo sos0q ayn any Jaqpon oye & pe x sm, (2 ou pum) « pe ‘x Sojrupuoe> amp svoafoxd ronecaidas 3 a4p 40} soysado vonDofoxd a ‘sna, 9 tra(errp 2 ( [oar B\e(eZoxd Pe Eee fos(eton (Gor oo eee]? y J pe solt0V%+ [ek +9 20(t0)% 1G 4649, we skengton Lee ecen'y 5 4 1 = (QE aAei 96 “uonemasaxdas Ty ap 203 « 2 Kou ((L1°S) uonenbg 109 suomwonddy sy pun Cx2ueuds sopa2q0yy ‘suusay uj soyes2do ‘uonoolo1d ee Pa K ee leh Po rp eT pp fe Ee 2VE) (Eee B JE) one ie Tp he anys sa fn aq uae 9 tg pud kak aq wet 8g faxing ‘uous 24 ve 1 aja amy worssys 0 001 ¥_ 008602 A\Textbook of Physical Chemistry 5.18 WORKED OUT EXAMPLES OF SALC’s AND MO's ‘A BENT AX, MOLECULE (EXAMPLE: H,0) A bent AX ole tothe pon grup Cy, The common examples 0 molecule ie Fig S181 1,0 moe wthcartsian snes on oxygen atorn Nature of ‘+ From the character able ofthe group Cy, we find th following facts, Irreducible and 2p 0) orbital belong to a reducible represenation® rece (0) ois belngt aes representai bial belongs toby ireduibe representation 2p,(0 abt telongs toby reducible representation ‘+ The symmetries of possible combinations of Is orbit determined as follows, ‘The reducible represenation obtained onthe basis of E G ot) 2 ° 0 2 Det ie is bial excange) (both te ota) rein nied posit) poskons remain vshifed) 1 ‘The use of rection formula o,= 1 ag HRM 4 i 1 1 i L ab) =4 Hence Peat 18 SALC from 1s ‘The symmetry-adapted linear combinations of 1s(H,) and 1s(Hy) orbitals can be Orbitals of censtructed by using the projection operator Hydrogen Atoms 6189) ols are used to represent iredueible representations for Molecular Orbitals of Water ‘Molecular Symmetry and Is Applications 603 on the generating fun Pamiany = ene 0 Yi)» WE have 1 Algo “The factor U2 the above ex rod a8 it provides the lative ‘ales resling from the operators, The abot vues maybe determine by he ormaliain ofthe wavefunction. The expeston of wonmalied funtion is, -4 angel Similarly, we have 83) a ‘The expression of nosmnal #2 Fenn) ~ Vien] ‘The molecular orbitals of H,O can be constructed by mixing atomic ‘oxygen with the correct symmetry-adapted linear combination of tytogen toms Mingo ors of reducible representation Vi Gino + CM ay,01* = C¥ia0* Gap,01+ CfVicny * ¥ ‘Ths embinon ids ee molecular olson svngly toning on sihtly ending and oe sony aibondng Mingo orbs of, bredctlerepresnta 6.18.5) (186) 187 lds bonding molecular orbital and negative combination with C, > Ce yields antibonding molecular orbital ‘The atomic orbital Yp,,) Acts as nonbonding orbital‘off joa we -@ = {yoq jo wesdep vogeaze0 a4, A pum °F srongio soy 4 Aly = 761g — OAL =A covers [A~ WARD =T8%9 + OAD =A anu oq wonopuosouds qgronpaun %0 fo spo fo Surat go otuioe Fupena &q parannsuos 29 eo “Hog Jo sTEEqO JenD=foW oH 2x9 ons anoge amp JO HRD WY Zs/l IOI aM aN ‘uonezmeuuou $1 suo orers a wars [oma Oma] Date smut fo sy ona 9 a8 1 onto ood be pwr 509. suonwonday 531 pun Karouau’s como2}op0 Sa JowesBerp wore.) vers a1 %yoq jo wesBe1g wonejei09 swoyy ua6oIphH yo s1euaIO Ss} Woy JT¥S uonasaida agpnpont 1 01 Bop (oay'de ue 1 ojduxs uounon ayy, anos we ow ° 09 a uo poureng vot sonewosaxdas ‘29 pay 2 "dna cap 302 Seay pmo e8rs A yoda oy sBuo}a9 2jaojou °xy JEON 10 ‘3 1dNVX3) JINOTION "XV HVENNT ¥ apron Jouredeyp wopeanse cers ha FH Jo wesbeIG “TaTS Sey m UNOYS s|JaIEN Jo wesBeNp wonefaLED 24, uonE}a1109 acruoyo roistyg fo youre, ¥ Hg605 A Textbook of Physical Chemistry A PLANAR AX, MOLECULE (EXAMPLE: BH,) ‘molecule belongs to the Ds, point group. The common example is ig. 5.18.5). Fig.S18.S Geometry ofBH, Nature of Irreducible Representations determined as follows. ‘The reducible representation obtained onthe basis of Is(H,) 26, 30, oo 25, Be, o 1 3 0 Tauber of unshitied SESE ‘The use of reduction formula a, = ae ncMCMLAC) gives + 20,0) + ) + BX) +200 ‘This also follows by inspection of characte table since the adtion of corresponding characters of a{ and gives the characters of reducible representation, Hence SALC from 1s ‘The symmetry-adap Orbitals of te constructed by Hydrogen Atoms esp by the expesion Be= DL, zcwrtao} 1 the coefficients of atomic socmalization procedure. Taking #5 Wy). 'e Bet ‘Molecular Symmetry and Its Applications 607 6.1816 +¥uaast ‘The expression of normal eal a 8.19) 92> Fe My ~ Woy ~ Ms oe [Note thatthe SALC 9, is orthogonal tthe SALC 9. ‘we may generate the 1.) The operation Since e” representation contains doubly generate or second SALC by using ether of the ori ‘By, on these orbitals would give ot sR .o! =F PMraig ~ Yay Vs But eter @§ nor 9 is orthogonal to gy However, if we take linear combinationa = (mA — CHM Ag] DP cg Anorats 2 war) lr ri 16 dagnunas Ye (ars) ‘swoy woBouphH yz ano paypom 29 WED andepe AsyU 2, pele=y sm <0 9 seni young) vonanpal Jo osm tL, © ( paurusun sueuar) ( pays 2 ) (ean na sreapovennewiy) a nego swonmyuosoxdas ag}onp xa pan am ‘ogg soreaeyo su wou “6 st Jo dnos® wed aa, (un :staiyxa) 31noTIOW “xy EVIOd ¥ 7 ‘ Sua sal cae won3309 a ers a Owe | = | | ey ya 50 wesbera sy 81'6 81g uy wnous 1 4A Jo wesFEP woneaLID a4, won ean109 609 sumo day 51 pu Kawau 00H D5 EA 9 + AD = suoyuase das aqgompoan We fo sponguo fo Sure an09 2p Um tyes po TMORION HL, SPE JeMOAION ‘woo Jo 98 Had ap UIIQO 0 PezTBALON 99 fet 8.TVS 289K yo seq ayer Jo Zupera £q paronssuos 24 ue> “30 Oa — Om Abe = paz) 900 24+ UMA = $5 4d = 3d ‘smoqoy se pasomas 2q wea £6 pu £6 ur sonnuenb Geurewt yy (cava) ws 1 ~ (e722) 800 =42 pu (E742) IE T+ (GHZ) SOD = 2 oxOH ‘ainpeoo.d aanewony ‘apne 99 sap Sow you “4 uonouny ay owt stnsas fd + § woneUIquOD 24), ZION, Aasyuaya rooisya fo yourray ¥ $09610 A Textbook of Physical Chemistry ee = 3 Mat (5.1825) Molecular Orbtals The molecular tits of NH, canbe constructed by mixing of stomic obits of of NH, 'N with the correct symmetry adapted linear combination of 1 orbitals of hydogen Mi of orbitals of 2, symmetry Mixing of 25(N) and 2p{N) with the group alo lads othe Formation of tee molecular obits Y= Ci¥a09 + CoVo5.09 + + Ma) + Ye 6.1830) Y= Ci¥i09~ E¥a,00 + Sloan * Vaca + Yana] Va= Gi Vos0a~ CF ¥ap,00 - CF [Yio + Viaity + V1 (5.18.32) Mixing of orbitals of e symmetry Ve= Cap, 00 + Cs [2 ay ~ Voy — 6.1833) ¥5= CiVa2,00~ G Maa) ~ Yaany) ~ Ys 6.1834) Yo= Cap,00 + & [Yigayy ~ Yaaro] 6.1835) Y= G¥y,90 = 6 [Puan Yea] 61836 Located ‘A molecule of ammonia may be depicted wit a eabe (Fg. 5.18.7). The nittogen olecular Orbitals of NH Fig.5187 Ammonia ‘molecule within cube Bach of the thes localized molecular orbital in ammonia may be considered to involve the sp hybrid orbital of nitrogen and Is orbital of hydrogen atom. These combinations may be obtained by the linear combinations of nonloclized molecular ‘orbitals as shown in the following Molecular Symmetry and Its Applications 611 Yoon, = Hit Met Ve = OW a0 + GY: 4G #26) HG-G~ Assuming C,~ C, + C, and Cy ~ Cs~ C; to be negligible in comperison to C42, we Vion, = Cans + Wap. + Ca¥ 1+ CM aga + (Cy + 2 18.37) Simitery, we get Yin, = Vo- Vat Ve Wagan + CoV ap) “0 6 38) ~ 25,06) COV ap, 00 HG C+ Cig 5.18.39) ‘The coneation diagrams of nonlocalized and locelized molecular orbitals of NH are shown in Fig. 5.188. HH 6 HHH, « o ig. S488 Correlation diagrams depicting (a) nonlocalized and (b Iocalied molecular orbitals of NH anaenaammmnnnstnannemsr aa ceewadsr'co0 RUE Ss'0'6TO"BS OAR ame UIpAHON?D pure 91D OSAEAAL noadsar ‘soxe-2 ue {ay noge suorBay ay) 2reyo da pring pur Futpuog sane 4 por ASA spenqzo zeynosqous ays, “aueH woHoxPhy ane} ay Jo yee pur tore oqo og usoaaq a8r0u> én pling pe Buptog st yenq302e]m9fOu OM, ting — ¢ a gy asera [° Gupooame) — AID — "EAD =k hg CHG CH A oss) abo + OAD = Gupiog Aly + AL =A Grar9 ferarsy [Cig — Ching 5 CHA. CAs 4. OMA » Gupwog HD+ FAL SA urar9 A= Cg — CHA 4 CWA Alt — “MASS = (Gupu0qnve) tag - “PASO ="A Dg — CHA 4 CHI ty 4 EAD = voverg [A ~ (Gupuog ALD + EAE = HH Ausrusas® fo songso 22.0 Gora [As CHAS CHAS (@upungnee) ovary [MAL HHIng Ona CtAy + OFAIg= (upd alg + Ayala Aaaunuds 'y Jo sjonqao. mmo ‘syeuqu zejaoqous 1yBte Fuysoyoy amp ony sywsas pounds syed 2p Jo woe ox@oxpy duyatoauy syeiquo dear? ap Wve sTewgx0 woqtes amp BauiguIOD “dai? ayp jo suonerado Knaus yor2 4 steuqio 2:09 Jo suonaurqumos se2uH autos oy 196 st suoHuNy 2524 Jo HED pu £19 suonwonddy 517 pun Canals sopo2omy yanoodsorsoreupuooe-? pue se mnoranyag Aapunaks sues op 2884 A pure aA soonouny om xn aazpuE? pe seu] 210s ow ‘249 02 Buopeq (9Y'8z pur (0)"4z “(OY stenqvo amore ayy -'e uoneivesexdes ‘2 oF s809}0q (O)sz Tego olwore ay, sf aueMout Jo dros rwiod ayy, aut sadses CHI pe CHS “CHDst “CDs “O)'8C“O"Ee “OY Ose am ste aOR 70 "Neuen 90) pateps00 99 ST Bay ue Uo jo TRO nse A, “panos en “Ul = "il >) Poe (2A = "zs “tH -) Cn — ‘en =) ert “ZI ‘ZA w aN sto vaBOAPSy aM AUN st 94N0 aA JO BU, po ay J] 992 9p JO oaxy a J So2o aH HNO HaNUOS sxe weISATED ‘m1 jo uo 2x9 2q 0 pasep[sveo st Ynys agro am Jo i099 9m Te sm] Wore vogue aL (GBU'S Big) agno 8 uN prdap 9 feta suman Jo 2729}0u8 Y ANVHLBW 4O LNAWUVSEL TYLIEHO HYINOTTON sreyqi0 2eInD2I0N1 yo uonewio4 arnosiowy Jo sreuaio eousyeA, atesout suey 681s Ba ‘ainoaionn 5449 40 wonodig asuayg rosy fo ORLY 9614. A Textbook of Physical Chemistry Molecular Orbitals of Methane ofthe tetrahedal symmetry, each ofthe bonding point ‘along s CH bond. The four localized bonding moles ‘obtained by the linear combination of four nonlocalized molec and yp, We may write it as y=ay+ bys eyes dy 6.1852) ‘The molecular orbital y; is directed equally to all fou hydeogen atoms, th vation in the value of a does nt direct prefreatiall to any one hydrogen. The molecular onbitals ys, Ys and v4 ae directed along the 2-, y- and z-axes, respectively, and thus the variations in b, ¢ and d help directing y towards the hydrogen atoms, bet eye de and, be th direction cosines ofthe CH, | rand 2-axes, respectively. 1s proportional to these direction cosies ‘is 2 constant of proportion along the CH, bond. We bet ey dem ell + miy + m= ex (5.1854) 28 given by Ba. (5.1838) wih With this, Eq (5.1852) becomes Ve, = avi tel; ye emys+ envy 61859) Since the above expres directed towards ¥-axis lows that, = cos (109° 48°72) = Wf v3. Hence yeu, = av; + (e/V3) (ys + vs+ HH) (5.18.56) Proceeding sila, it canbe shown that vou, = avi + (e/¥3) (ys — ¥s~ Yn) 6.1857) wen, = ay) + (e/V3) © v5 + ¥s- wd (5.18.58) von, = 2¥ + (e8) & vy~ Wor wo uss) rege tn ‘The corelation diagrams depi Molecular Spmanetry and Its Applications 615 These give a= Land e= 5/2, (1860) ‘With these, the expressions of localized molecular orbitals become Vou, = vit SWs+ vst vO (1861) Vou, = bm + PVs vs- Wd 6.18.62) pene oar, ene Won, = Fv + FO Ys Yo# vm (6.186 Substituting the expressions of Yi, Wi, Ws and yp We Bet oe ven, * Limo + 2 [Vines # Vania + Va (2-3) G4 ‘he ei sonst eld elation tae sown th GaGa aC Seting C,= an C,~ Cy he ston Yn, teomes Proceeding similarly, i can be shown that 4 Ver, = [anes + apes ~ War, ~ Vancr] + 2G, (5.18.6) van, = Lanes ~ Varses# Vipjos~ Vasc] #20 6 c= FE [Vanes ~ Vayo~ I ] 26 ¥ ‘The localized 'moleeularorbi 2p{C) and 2p{C) bias, is of carbon atom. include equal contbutions from the oaized molecular obtain Bail 1g nonlocalined and localized molecular of CH, ate shown in Fig. 5.18.10.1s wonoas 295 LEO = 7 =" pur z999 =" = ed eowwey>our-umuEN Yep a, sueIsuoD are YD pue o Xo ty roy wears) oer) ears) usr varpring-swtus Jo suoreuiies "y om 24) pur suo (evar) (ars) usr) = 4" ane 38 Ag oLsi's) 0 "We = ++ {Wo} CONE + ('egen"ex + (er) Coy'sx + {18g} 138 08-9 pu 9g Soanaad 430 srmra0 *8¢ 90) uo (y(HN/24Z=/g) rosado uonsafoxd yo 250 au jptosaide) pu | stogiea ‘asqns yooo wos) au0 SuPye st no 204p 0190 ng saNNO YEE 01 WH ay. Ajaaneadsar“G po % pur "9 pur aro) 20 sense}ou MUDD 244 98 ibe Knounss ar yoe> Jo sIogWau ‘om oy sjruguo "8 sno} a4. "verfac= "1 ‘som sons CUZ OO" = '» ejnuuo) vononpas Jo 980 3, 119 suowoondy si pu Kuruouts semen ‘uajpeing “sues J0 8,001 swory woqed Jo s1e 1410 "dz wos) 1S rE (=) 7 ' 9 suonewwosoidou . or 1 74 mo} Uo poreg orNtaHa! aaFNpa! AL 1 2anten ‘815 1g) suopema-sueuy yo dn0x8 wrod ayy, SNSIGVLNE-suest 40 STVLISHO HVINOTION- ONY S.01VS tl Aasquoye rowkug fo oomney ¥ 919618 A Textbook of Physical Chemistry MOLECULAR ORBITALS OF NAPHTHALENE Nature of ‘The point group of naphthalene (Fig 5.18.9) is Dy Inreducible Representations ” 8 L Fig 189 4 O 2 [Naphthalene motecoe. = Therdireciens pecpendicular tothe ‘ 3 plane of molecule crs ‘The reducible represetation obtained on the basis of ten 2p, ocbitals (which point {in the ditecton perpendicular molecular plane) is stilted undergo reves shied in dection in dection The uso of reduction formula a= (Wh) Sy 68) 2) aves Gide iow) ote) o a -10 ° Alltheten Alltheten Alle ten Eight cia cxbials are obits omit are ae sited, Molecular Symmetry and Its Applications 619 Hence T= 2B, + 3Byy +2A, +385 (18.78) form three subsets Subset 3: gy and “69 ‘The members in each sub tals, and we apply projection operator on the orbital (ubset 2), respectively, and s0 on ie Katte -05- 944+ “he nomalized SALC is Pp, 92 = 10) e+ Ls ¥2 = 2lp2.- %6- O1+ 95) Meromalied ALCie vie! fop= pe- O14 8 csiss0 By Paer=tMer+ ie WS= 20-054 Os ‘The normalized SALC is (asst) 90 +6 anon ie, ¥i=2e2- 954 01-931$9010 5 age wt unogs ane = y Jo dnon8 270% 0 o suo usaxdan ojgranpaun ap "9 Jo Swz=) UL Trot lox a (2a) = (yrnaino = nae] = f2 *A1s901490, ers) Cymgyieo = "9 ‘dnoup an10k9 @40 Ienmauodxo Jo 2sn 2120 paseq st sty, stionequesaidoy ‘ygenene sy dou aaa» Jo suopmuasasdas afqfonpaut asa oy auay>s BOUOB Y ‘erqyonpent ¥ 8 JO YORE “y= eng i ara“ sauswy?q pouyop sty opi0 so duos a1f49 y yo a WOY Si} ap Busn Kg poe 2|rDB|OW ap JO toge Anaunnés TeooMMO: and ip Sus £ potannsues Apse9 9q we aINHOME ‘2upfoogse # Jo suo woqi jo spag30"d HuAJOANE ITVS MUL WO 0s pe HD 49 “9 apne seydarg sted moojou 0 Uonaau pope 1 wonyaja-u_w sone ajnasjout o9KS0939 woishs “gt 81 suai apoooqme Jo eu syRSOIOU OH, aujokooaue9 WALSAS OMOADOAUYD V 4O SIVLISHO HVINOTIONY 6i'S 1 Jo woe woqse> (12's wong 295) qo seroojou a Jo uo|ssxdxe wonezruso am HM BUTE bo sejoos Buxpuodsauo2 ayy Ut 940 Aq 900 $9:8:90asoqy Se ‘eaez 0 onba nsw aU0 Jo ween. Jo yore Sumas 49 pourwarp 2q ue suo}eHquIOS axOgE aM UY sata 209 a4, ser Ally +8 AlD + Bal = 8H Auman (163 " nouaussy (ossrs) a sours er fh sours 129 suonmonddy 51 pu Karounuts sopnom0yy -auyuoy sesqenquo snooqou uy ‘au. Anon aes 2430 some ouojennuden “suze Jo sfexpozromjow 2x83 pourqu0..9q Kewr'eA = ANA 8 TVS OU, seo Gear 16486) 204s onys porpeusou aa Pd t= oy user) (66448498.486) Beth sionvs pmo ou, O48 +O += IA OT D+ -0-)+ C8 M1)+ 4d M1) 496 (+26) = 8)" orars (8448456418) Lath stonvs pease ou, P+ +b =tA oH aq +r +16 (D=t0%y Geers) (8-18 78 + 7A)E YA Sots poemeuoe SB +e tA 3 (0)"% ser) (6% +12 = 94 st OTS poatemoG oy, A856 416 =IA 34 =ioMy ty (ea no 9a) = 5A sory ponmut0n (8-8 =5A oy ears) C4 ~16.498-%6)% =I stonyS paryeaoy au Kasnys wowiya fo yom, ¥ OggMolecular Syrametry and Its Applications 623 622 4 Textbook of Physical Chemistry Rearrangement The representations shown in Tae 5.19.3 are earranged a8 shown in Table 5.19.4." Rewrlting The representations given in Table 5.19.1 consiute a axthonormal St stisying Table 6.19.3. Table 6.19.1 the expression Table 5.19.4 Character Table of Cycic Group of Order Five all Ur (5192 ‘The representations shown in Table 5.19.4 can be written with snaller exponents using the following facts, chee CP =k hsm times and Cf = Cf CE Gh = ‘The resultant represcatations are shown in Table 5.19.2 advantage of using only the principal axis rotational symmetry for 1g molecular ofits. with rotational symmetry Cy, there sing to each iereducible representation of lustated by taking an example of benzene always be r0up Cy Ho) ‘The reducible representation of benzene based on sis P orbit is as follows G=6 Seq a-a Rewriting Table 5.19.2 (5.194) ‘we can write the representations of Table 5.19.2 as shown in Table 5.19.3. Table 6.19.3 Represt ns of Cyclic Group of Order Five -e ne ‘ota sym repesettion sw represemed'y he smb A. naning presentations are ich pir are complex conjugate the elements of one owrs) CO ~)gp = ‘5 ((eara) ws re) + % 80) (663 ~ 83) + 7962 - W989 + "059 + 16) - ofa +t059 +g! = [EA (orers) ares *ol(Grag) 500 2} +*9U(€/22) 9097) + Ide = 2A wo8 om (ert) ms 1~ (e742) 900 = (gag hho = $2 pu (ea) ms 1+ (G212) 800 = (gngydro = 9 aos +94 M2 242889 +16] = oA 2 298 9 gy, (ors) Gers) Sheth ata Saonrmga sug Huymojoy on aye SWofog|E09 fas Bsa 9 AIM oY, “siueFoIj909 AmmUVFeM anjoaue GA pur f gues argue 2x, wors) ot (ors) wera) Oy" + 9g") 10 zeInosJow TuImoyoy xp sone (to. yeopaUINL weISECO esodo uonefoud ax 40 6% ST9 suonwonday 2 pur Crouaaks sopsapopy B= J0pI0 Jo weIshS oHDKg Jo aIgeL HEED SEIS GEL, {61'S de) ¢ = 4 19pm Jo wersks apaKo ap 40j2}ge so.oEaYD OM Bu Ke Pepnnstos 9q un sto 9am ayy 30 oneuqui maim pepe Crum o (61'S up teng30°d anpsedsas amp ance ou0 64 Nog ye Hf yous sePaROR vse Ytodondoraa oa, ‘AN3d0WdO710A9 SHL 40 SWLIEHO UV INOTTON $8) + 820) 4 8>)% + WO) 4 66)E + WE = ‘POUGOPE OSD + WDC ONT + gaye = 64g Son sorted wonoofou jo 2en si, wonewasasd yo erbuto mnozou 5 3 eng sepoofou Ng 2m 28 Snoge a TENN SOW OVOIL a J swarouj09 a are dos8 po sae 2 nev om ‘sous ""*B *3 "5 1g “aera 10) s9pN0 RUNHNoD ay Suonetodo say yo ovo 26 ae Sala p10 feuestm Ut oyn fy 9 daos8 ap yo suomewosaids ag}onpoin "13° Pe or sBuoqoq sno HPD Jo seq sHRo>qour x18 a JO YEO « Notmodo g jo eq woaia one sivas G *8tonpour snowea jo ssareesey9 iT pow 9 = (3) 108 01 em Soo a0 eH 38} taelgsasyou 2p puy 2 “suopeuaraados "PSI OI paajosas 81 aAoge porst, uoireynasaidas usdoadoptsj0 sO Vers Bt SOWoin jo suojssaidx3 V1 ‘Suponisuog 10 fp resou05, asaya oeiyy fo yoga ¥09626 A Textbook of Physical Chemistry ‘The three normalized combinations are vi = ROi+o+ 09 6.19.2) vP= 0H + 6-99 6.1913 VP =O 09 6.1919 MOLECULAR ORBITALS OF BENZENE Benzene isa carbocyclic system. The cyclic group of order h = 6 (see, page 623) can be used to built six r-molecular orbitals (Fig. 5.192), Fig. 519.2 Benzene Molecule Hence, Hence, Hence Hence, Hence BO. = GENE 61 + COC + ACCDIES, FMC + Cea (CHE + CEKCDIG = (Hs + (te + DA, + (D4, + (D4 + (D4, Vi=Oit Ort 14 O14 0546 619.15) Py 4.= D+ DO + H+ DF + (Dd + Dh Y= Oat = O18 OM Perot = DO + Pn + C+ EDA + 600s + (ENB 19.16) i= I+ Ceba~ Es He 95 + E16 (619.17) Paar = (00s + (082 + E+ - Dba + © DOs + (Eds VE= Ot EW EPs Oe E105 4+ Fah 6.1918) Pent =O + C2092 €08+ (P+ EES + C06 Vi= 91 Cha be bs4 Oe Cs Fab 65.19.19) Molecular Symmetry and lis Applications 627 Pe,iaba = (Bs + © Oa + C &6)3 + 1) + 65 + CC), Hence W5=61— Fyds— 000s # 84 eae 6.1920 ‘The molecular orbitals involving eal coeticients ae obtained as follows Y= Vt WER 2 + (Cet CDM — (C+ £09328 (E+ ED, +eet ED = 2p; + 2e0s (2n/6)9, ~200s (2416)9 ~ 244 ~2008 (2n/6)9.s + 2c0s (26), = 26+ 62 5 261- O54 % (61921) 1 ee= e682 + (65 es (C5 © DOs (o£) = Hal sin (2n/6)9, + 21 sin 2316)6, ~2 in (2716) ~ 21 sin 2n16)9,) 7 NF 12+ 6- 5- Fa 19.22) Ws= Ws + Wo = 20, Hee + Ee), Ely + Egy + 20, AR + LDDs Het Me = 20,- 92-054 We Os O6 (5.19.23) Vo= EME wee Cada ~ Co~ eB) # Co DBs — (C6 ED Oe) Fb Ot bs- 6 : 6.1929) Finally, the mokeclar rials ae normalized to give vit = Lip + doe be ee 66460 ws19a5) Va) = Fel1~ 02+ #5- 844 65- Bal 6.1926) WalE) = FslH + f= 5-26-04 A) 6.1929 alBi) = F164 65-65-00 6.1928) WE) = Fg l24s~ 2-05 +204~ 05-4 (619.25) VolE) = F102 65+ #5~ Od 6.1930) From the characters of the operations Cy, C3(= C3), C8 Cp CL (= C3 and C$ sssociled wit he group Dj, (10 whieh benzene belongs), iis obvious that the representations A.B, E, and B corespond t Ay, By Ey, and, respecivey.-y tore pen029 99 w0 SEHHO (L0e's) Pao onransens uo yoqyn aodsm aq pousigo st (3 st pty) Neveu st Jo 2e2AuT ay 9 xiNEW =n us pouwop! a9 Kee SSyIVS Ww uo 308s pourMD aa {TOTS “HL 2%) snonprguls ou poype-knpunaXs om (SOF WopLAd A JO SEABED =a 20 y wore fend ap Jo EHD pay aM GH PELNHON! 29 fom asm) Sri oes Jo 9s © wuo}suE 0} pas st abrayse oedo wonofoad ay 15 Jo suopssaudo “xen yrvofoquo we swasaxdat sone ain gf xiuew atp Sursodswen fq pourege oq wea 3 xaneUr Jo asaNu aM 8 wos) ‘elf woes “ay fo ea [lo ‘2804 2m ‘suoneou xine aM UT ows) AD + "EA 4A = Ba Gos) Bay 4 AMD 4H = BA word Meaty 4A Ty +A = MA “amolfoy se parasaudas oq Ceur spnngo pugsy ,ds woqearnbo samy 244, “Teug20 £2 01 posedwon ve A@iouD sore] yon ‘nee sTmeo PE at 9901S papnroX® 9q AeW! HD, Pu SLD “HA 59[099}0U 20} p+ ep +520 (uonezpLaKy ors) ors) sow swoqy 9 ave pur Ly Jo saseq amp wo Hom 1 anaoye xp exp uy 928 Eq dros yod axp Jo a}ge SIEEYD om WOH, os) ates 629 suoynonddy sy pus Kyou soyno270H1 axa 2 Sy ayo2jo0 24 comowtn’? 4 ato Si aorssoxdxo ap Bus f patares 2q veo *q dror8 wood aan Jo suoqeynasaudar ajqronpant Jo saszy ul Vonenuosaidax a}gonpot Jo worjossx 24, 1 xn eam 0 Fo ‘oe 0 oun aie s09%4poogsamn wy SE € yey menor scan poonsampany SS payin sous 1 sree vormos i Bop 0 FHI OE a Faysa siooe ogaamnapIV Oe © yin sus S38 poo 888 9 30 WL a ae ‘ions palin aqua —_vonoiedo Sq dno1p qwjog oun 01 BuyBuojoq a7n95}OV4 ay 40 sio¥20q puog uo poseq uoREUEsaIdeY TaIONPEY 07'S OIE, 102"s 21981 OF umoyp st %q dnai® pod a Jo svonezdo Knounts 220) starseseyD Jo 125 10928 puog payiysun fo soquone 21103 yonbo sj uoyosade Caounuts» fo uoumpuaseidesayqrmpa Jo 21901049 D4, ‘money se paris aujoprn amy qo patio 29 fom sx1san puog wo posng voneiwasaidasofgfanpas Jo -Rrsexp 2,421 0 [Bnko2(Bue poog eo ts «sto BA spreNOL HM sTENGIO Sex "V wot Xp Jo S]eNRIO PIGKY sp —Ap HER apIoUID sHOPSA pug ays CL neu yurod 24 of sBuopeq (oueyd Ae xp w 29 on use) ayMoojou Fey URE a, aus a yo sjengyo anuowe Burtu Kq pourene st wow we 30 sjrqno puAKY au ‘STVLIGUO-9 SNIMOANI NOLVZIGINGAH ia seue}g jo ojdurer STVLIGUO GIEGAH JO NOUVIUOS 02 Aapungg yosstya Jo x009eaL ¥ &630 A Textbook of Physical Chemistry Fig. 5201 The equivalent orbitals of tom A and atoms B orbitals of stom: 9.51816 (a.5.1817 Watton a3 (4.51818) Interns of hybrid obits centred on atown A, ve wl gt +95 * Vai] is20 yP = Fle : 5.208) pa WP = elgg 5209) ‘The SALC yj may be identified with yyy a8 both belong to the A representation. ‘The SALC yj thay be identified with the opersior asboth remain unchanged on applying The SALC ys may be identified with yr, both change sign on applying the operator 6, Hence, we write (520.10) 4 Yous = FV Was *¥, Vans = Fe ¥g — Example of Methane Fig. $202. Methane molecule Molecular Symmetry and Its Applications 631 (52012) From tis, we get lve] [4 iean2) Vas aK eae -|2 =fL LL | Nye, % BT BI" jo Et all lL Be IL™. ais vg devas By, san) eee 1 7 FM Het hve, (6.2014 1 ot 1 1° BY Tee, Be, a The structure of methane can be drawn within a cube as shown in Fi ‘tetrahedral molecule and belongs tothe point group with the four hybrid orbitals of carbon and pont towards hydeogen atoms. The acters ofthe reducible representation based on these vectors is shown in Table 5.2022 * GS ty(AA —W)E =r) (AA +A 'A)E =A) woremiroider 2 (Oh -7h -98 +'A)E =) CAA HAE AIA uoromicete soy sam a0 pgs 240 8 eaEDHONL 2H, Yay + Ay Ay apap + Ay =A} onomarsdas "hy "hp Shy + Ab =A +A aE Fag +7A9 +%h9 + %Ag = 1A =A onomuasoudos ty Par "A9+%AZ—"Az—= YA Aarons comm syns 24 wo “hy yo wonrondde UL, + Pac 7AC— Ag +TAZ~ =A anon ty ‘ovat synsaz A wo ly Jo uonsondde ou, + PAc—2e AZT = TA Kusounuts 2 ‘nu mmas A wo “y Jo wonsonée oy, © Ag HAD ESAG +YAg =A Knounuts 1 comm ssas "A wo Yq Jo woneayde ous « smonoy sear woqi Jo stag pug BUNATOAUH TVS 30} UL, “ow Hm 4 A tA AL A AWM AM % ~ A | "A "A "AAA * ww | % 7 Po % * as 3s 7 * ” Am A tA OWL ‘& ” ‘ow Aw] sa w th A ata | 4 % 5 5 De 1 dnosp wrod oun jo suopeiedo Anowuuks, ‘yj 2pun uoqieg jo sieKYORUGAHJoUoNewwOjsuEN EOS O14EL £9 sontoyday say peo Kasounuts s9n22,0H4 se A@ioua ve yor 4 VoqNRD Jo sTRNQIO PE =Kp 28 papnoKe 99 SoU Pe ‘auaups a zasamoy| (woneZPUGKY ps2") “P +" + P+: D+ 047d + sags san Cp) pmo Cd“d") tL soy 6 are suonmuasaidat 2, py Jo seq ay wLoy YoIy steno arom ain re pug 9%, dnos® od aq Jo ajge iroeey> ain tog tpetye"nmyssonoyy % og cue “is 7 é ¥ DOB + (VOB + NOE + Is 18 = = smoqoy se am wonemosoudar ajionpar axp ut pauiue> suorrewasaiday afqionpauy a z Payiusen oar umd uonoogay an Sun Hoes om "09 ° ANS a Spuog a} HT 9 o ous a spu0q 0} om e pogo sew set 1 sooner om ae Seppe 394 PUP ‘og * sun sues spo 00) 9 a Ee 2Mn99I0¥4 "HO J0 S101900, puog ou) Uo poseq uoneueseidey aIqionPaH ZOzs OEL Kaasyuayg porskud fo WOVRLY TS634A Textbook of Phyzical Chemistry ‘The wavefu representatio fon yj may be ident 4 with Yay 88 bond to the A, "The wavefunction yo may be identified with W,,cc) 88 ¥4 and yj have postive components along the +2 xis and y, and yg have negative components along the rans ‘The wavefunctin ys may be identified with Ys, slong the +x axis and yp and yy ha 85 Y, and Y, have positive ive components along the mt va tay be identified with Wp, ¢c) AS Y, and YY have postive ng the -y axis and yy and y, have negative components along the ‘Thus Vg? 3 Vat Wap, + Vay, + Wap) = $V Yap, — War, + Van) 1 Yag = a Vag, Wan, ~ Yan) L Yigg = 2Win~ Wap, + Way, ~ Yap.) ‘Molecuar Symmetry and Its Applications 635 HYBRIDIZATION INVOLVING x-ORBITALS EXAMPLE OF AB, MOLECULE ‘A roital is defined as one which has one nodal plane containing the bond For each B atom inthe planar AB), tee are two 2p orbital (namely, 2p, and of r-natue. Of these, one i inthe melecular plane perpendicular to AB bond andthe second os i perpendicular the mele plane (ig. $203). These the appropriate directions and ae erred tous nd an a Fig. 8203 Vector representing orbitals of B atomsin the planar AB, molecule ‘The two sets of mocbitals may be tested separately as no vector of one set Is interchanged withthe vector of the second set under the symmetry operations of the group Dy. Thus, each ofthe wo sets may be considered separately asa basis a for a reducible representation, Reducible ‘The character of asymmetry operation may be determined based onthe following Representations A displaced vector contributes ze. ‘An undisplaced vector without changing direction contributes + 1. ‘An undisplaced vector with changing direction inthe opposite contebutes =I ving are the characters of recuiblesepeser Irreducible Representations Formation of x-Orbitals oP) ad Gp 2d,) AR,Pao) + AE) +5H(0) + ACD) (A= h 6A) (AA A+) nos 'p Sus kg porn 99 Kt sa Spon sors HE" SIENGHO PGAH = ep 3594 pts am EP Sous weve a 209 onewiog ese gy soem UL sors-4a oz» 0 oo eo 0 ¥| a a a ‘money ss sono pg ane sy Uo pasegwotretassxdat ajqanpas ay, %q Anos oun oF s200}0q (¢02'S Sta) "AV e¥re=four seUEKS 24, vuonnjos sSuypuog-ar wt woneapanhy ay aeae omy “mou Fay mee 2 swore ano ap um SSunpu0q D 2H PANORU Y MOR Jo SEO PHY KN HEY 49'S WHO]AOAA 1Le9 uojoonday sy pun Crrunuts 29m22)0— i naaqou Yey ut pouey ‘am sed gy wis om Zuoure Ayenbo pareys spuog-t 2anp xp 11 pres 29 eo uORPUHO} Spuog-r aN UY pasn 29 UeD W WOE JO sTEHO P28) a KU) swore gf i puog-x srendosdde yo sd ayy © owes ¥ wore 30 sqeno d mg “g sO spuog 0 Buqunoy ut pasn uooq axeq sna V J 009-1 —Y 2h a tp 0} {wy spu0g © Is Bumi6y w pasn axe y WOR Jo sfenquo ano AIS aouIg « sieug0 ‘jnsa}ous SAY Ws sBuypu0q'! 305 WEA 29RD HoIsR;IueD FUIAOTIO HL = 44 O UONEULIOS MUM 4 suopewuosoidoy ae pons 2q eo 1 018% Joo SERN HP WOH, ‘taronpa.s} oo 09 oo wo 0 0 fog ‘oc fsa '99 9 Go=2t "99 D9 “OR ‘noo 9 ae woe) Jas jo stoner ay, "vonewasoilas ney (wore o soup ose PUD) su. “0 hos wed ay) jo s3p0ue30 suoReyuasoudey 0 33 Jo ye Wt poRUENDAD #0 HoH ‘jaionped, a en “| <4 dom snot a A aon rics a /\ AGT a a aK NOHL 5 pur & 9 "ty sara1y20o Jo sonyen ai softoud requ sejneafou Jo voysoxdeo uopezeUNON 949 wore Suope suopienbe mmjnoes wr auO q auo sarRau9 soy FuNMIEGNS wis du91-9 = 9 9 9190-9 = 4 dai90+m=4 dsigi+neg ‘soon Surmoyfoy a 28180) panjos 29 ‘ro yon g ut end yma} 0 woyssaxo we 93 2% SusuEIp snp SuHUadO uO, 19 suo nda 1 Kaas sopzqoyy sorysbusn Aq uoneoyyduis, g o of -2 do od ao d 0 ¢ anol : soup 2998 aq wont are ‘snopuasaxdd joxeNH 29pun Tego syMaeFou 3 SHOU a, ero oF eT} V) 109 45859 1889 #18 = 084 se qmge eau 2 a pon 28°C4'1°§ 3D ape JO AIOE Facer seq oe pose 2b 18 se pasa) seu "0180p 28 ies) serpeng sue TS Sth ANBIGVINE-sue7 4O NOLWHLSNT dnas8 ou0d ojoagou oy fo wowonassuds ayyonpus uns oy 0 Buoy emu pu'A oR soo) st aye orezuou tue esto o yo wouoqun a sou wonenernds 9 G.npan ums 20) Buoray/A pon won wus Kuo vorenoranas oneanuts SO: PRK Ms ompoxd pups, /A pie suey a9 Jo epold ap 24 a oume> ‘ogenustandan sy vo spudopre8oqu asoge an vf paeufrur aq) 0 Asausnds ‘au uonensaida ints Aan a 1 S800 etaye Sea on ssn] ap 2005 Beato sono syenqpo ap ase A pre 'A pus syerodo wemoxrueyy st 8H AIH 1s) ania “n'a f =H siommnoous avo ‘yngofou #30 ure ue Uy SaxRata onsan22f9 JO ensruoyo wumyuenb yo suoneosdde Kuen ut seedde Yorya sso ponfoxdy 300 oy popiatis oq uo uogezesaue8 oxoge a, anes O00 at amy wa eS = OOF 1 puna nea 2 ‘aoge np Jo exon mp uatn "ef = ef 3 suoent Ss pononuy 1269) Aaaspuoyg posted 2 4oOazAL-Y 02. A Textbook of Physical Chemistry Similarly, working with other matrix elements ofthe first determinant, we will Bet Hy=a-B Ha= Hy =B ence, the first secular determinant becomes \F =0 where x= (a EVD a “This gives x66 foots are x4 = Hence 224 21-5 Lp 2 a+ 00188 621.10) p72 a-b 1 aa 2B = Ba 0- 1618 21 nr an a 8 Similarly working with he second determinant, we will yx a+ 16188 and Ey= a-06188 (21.12) ‘Substitution of these eneeses one by one in the corresponding secular equations falong with the normalization expression of molecular orbitals provides the Cy Cy, Cy and C, iw Eq. (521.7) For example, for Ey = a+ 0.6188, Cla~) + GB+ CO) + C()=0 or Gyler~ (4+ 061889] + C8 =0 or C= C0618 Subsitsing this inthe expression C+ Ch= 1, we get toaie) * c= Ot = 958 sos dels * O68 Hence E,= a+ 06188 =0.851y; + 0526y, =o. ssi[ Fee - 0] +0526 [aw - v0] = 060219, - 9) +037R%- 3) 21.13) Molecular Symametry and ts Applications 643 Similarly, working with other energies, we wll get Fy=a- 16188 yt, = 0372(9, ~ 9) -0602%,— 9) Beas isp yi 621.14) = 037209, + 94) + 0.602,+ 9) ($21.15) B= a-06188 vib = 0.602%, + 9) -037200,+ @) 21.16) ILLUSTRATION OF NAPHTHALENE Working for Molecular Orbitats rand ¥, In Section 5.18, we have formulated the molecular orbitals from SALC’s of ‘naphthalene (Eqs 5.18.79 to 5.18.88) In the molecular orbital treatment, the secular determinant of naphthalene (ee, Eas 5.18.89 to 5.18.92) Dyomner ts Joo eaun oe mete Meo aun Hey ne fe leo au Here, we work out the molecular orbitals yj and itals_y; and yp. The remaining molecular orbitals can be worked out following the same procedure. We follow Hilckel ‘spproximations while examining the elements of secular determinants. These are (nitgte) =e : and (p1Hy!6,) = itv andj ae aeigbouing atoms =O if andj are nonneighbouring atoms 1-95 Ps + OH (1 ~ 03 ~ 9s + Pe) + (bs 5) + (9a gly) + (ox Hoge]¥ . CICS yw onogs 3 suo Aevum ou, dod od ao sn mmo eae fo eH (coed 29011 suns) svengo(oSoear sour -yoe(ou ap 9} Saave sep pn AO sg ASN SNH A 0 PON C8 + Dive0- +B +S + ByLr9- OH + H+ + DoorO= "A seogt m= 0g lb + W)g0H'0 ~ (1b +b +O + H)g0r'0 = Oh . give 18 +9) 19¥0 + 1d +9 4% + BierO+ (H+ 479 + 'B)IOCO="A deoee +7 =! karina %g (8-9 + ~%)szy0~ Cb 9 +49 — 'A)eOTO= A dei91~m = 4a (hb -% + % —D)eo70 + Od - 0 + Nd —'d)ezHO= 9A geor0+ = 89 Saomanss y (%8-4H)19¥0- (9 +% - -"Sy1Ez0~ CH + - "9 ~ BIOCO-= IA seoec—m = Cd —@)g0¥0 ~ (4 + 9 - ~*S)g0P'0 = 1A d-p="9 (8 ~)LpeO+ 6S +99 - —OYPLTO + 89 +1" —'8)OOHO =A sort += y Looms %g soyfoy se ae sounsunks Bureuad 2p Jo suon2unyeaen pu sofinu9 aq yn wos 9 CRD KUETRENS BUEOg, (6b +B ~% ~%8) c97 0+ (8 +44 ~%~ 'bezy9~= [isos 6-96-07 aso [ts 1-18-92 bsso-= $Agzs0 + 'doswo~= tA + Aly = FA som, Sr9 suononddy sy pu Cyouaus syno2yoyy aurngornio 0680-= zs) @I9T = DBI9TI='9 2H -svonhqameni } od y vies 1=D+o9919 © I= b+ 128 an A Jo uonezjeuuou ay sg 0= 9 +Ga190'9 raf on "999100 = 920d & sigt-=sig01~= 9/9 (8.455 14-18) coy0 08.419 -%6 — 0570" [co 19-94-50) FJoso + [ray 4-14-10 Feo aosea+ Ages = tAig +A ="A sm Ses0 = (oss OxsI90) = "18190)= 19. HH oso (aI90+DIS=] = I-b+0890 © 1D va om 0A Jo uopmaysuou 2 Wo od +(u191 19 pon qgig1 +0 = 19-04 « o=@-"99+"H'9 0811 +@— "9 She sven sos vonnjos, Fes welqorg si90=8191 =29'9 31 o=@-d+n¥ors'o o=doe@-m'9 91 ot Eolas deivo-v =49 8190= oe fae eeen ents z z = = pe al-=y ah 890 paper TS 985103 oxt-tHe o=I- tar 198 of yueuen2.9p ap BuodO) E clr yg pele at? 2 | {dna -»)=* aun) =|! o-f gael souod9q (11°17) ha Aq want se weeurtap sey OUP 95H UAL gto= 2b Pn 8) +66 fam) + Cd an Ady + Fan) + Pen) +00 n°) +H) + GO PNT (66 418 90-1) Mi (8 +169 8) = CA MIA) =H Som 6ujurewou yo s91610U3 Aanseuon posityg fo YoOmrAL Y $95 A Textbook of Physical Chemistry 10 Sets of 2p. bitals aducible presentations ‘educible presentations ormation of ALC's [Each of the eight carbon atoms contibutes one 2p, otbital towards n-moleculat tals may be divided into two sets since the orbitals in one set wbitals of carbon atoms 1,4, 5 and 8) are not interchanged with any of the is in the second set (2p, 3f carbon atoms 2, 3, 6 and 7) under the symmetry operations ofthe poist group Day. The two sexs may be treated separately (0 work out SALC’ the reducible representations are a fliows, 2G 2G i 2% 2,20 . 2 0 0 4 0 2 0 2.0 0 4 0 2 the same type and numbers of Hence ‘These may be generated by considering he symmetis of the group Cy, We ignore ‘ultplication factors as these aze ascertained by the normalization of SAL AaySymmetry + UCC DEO, Ms The rommalized SALCis--yj= 416+ + 05+ 6) ‘The operation of F, on g (otis of Second se) would give Peo x Ve= HO H+ 8-6) Molecular Symmetry and is Applications 647 E, Symmecry 165+ CO ‘may be combined so as to involve real coefficients, Vs= Wi+ vé= 26-265 ven TEE wag, 2g, The normalized SALC'S are We BO w) v= bw) For he set2, we have ~ Y= BOO) Formation of are obtained by mixing SALC’s of sppropriatesymmeties, Molecular Orbitals am CM + Gy = Gust Cave Fourn® CW + CVe+ Coy + Ca¥ Molecular Orbitals Ya (atatata=a Ha = (Wi Vd) = L161 + Oat 05+ 00 = E140, 1 9 + (61H 6+ Ot Ot G+ OD 96) + (5 = 0+ B+ B+ p=B Hy= Hy{ saty 24> = 95, wr S038) SIH om lg-> og 0 0 fo 3-7 0 0 lo oOo g-o g fo 0 g a-a 128 am "> 7 wow pur Fy «> by aBung> ay) no BurKED ly-» 0 9 0 o mp o g og 0 aa ol] * jo @ 0 a-a a-Si geht nS nan FH ee aun am F2°53, sen. TBseIOR a 04 9 = +59 "er O- CH —9 +19 TET O="A 138 non Ypiye—0 =" J04 68-9 +59 - WEL 0+ — 4 —WeOPO= z [9-294 8-"Elese0+ [0H + 19-1 ‘sm 960 (E9E:ONDIFD = "OMIT =O sscu=t9 = 1=]9+ Coro © I=p +9 138 am ‘uopoe woprajeauoN 9m wos vipt= rival = "249 = o=s'0 +GrIv0-KO soui8'9="y "9 +(q—"W'Dwonenbo moss an Yoryo + ="y 40a d dnve-9="7 tingly Srivotm= | & pirgs <5 SH IPE TEx & Qe bate FE Ose Be SOAR omy 699 suonvanddy 51 pun sourus sqn22}099 wus, S1eNg10 2e;noo}O¥ ave 90 4, sunouny 2930 (949045 + 9OFO- OH +9499 + WaRCO= SH 138 yuan fpupro-2 = 29 204 (9 499.459 + Wear 0+ 8 +5 4784 T6TO= PAREN an nce ard as 049044 4) Efoas0) [c++ 7+ Ffeseo Wig Alo = a 0010209 OW ALL ACO= GOOD = DtrIrd="9 W602 © 1=]9+,fIO © I=p+D 198 be ‘OWN J0 WoneaAMOE ap IO nro= riven = 99 = 0-8 +IreII sand 9 = "49 + (@— Ngo womenbe sinces on prc +0 = ta 30M dyo-oz4 = preg cap =! ret gelyetmaty = ahah nH ON Pex 0si-mte et OF beter soni uo i Foe cm FYE | co getter? of ger MY OF gga souuoneq wrupa}p JERO98 ae asa NA fe+n= edededtosgeden ed sied sol = (4 EI 9) + OO BTL 4D) + CO Me PD + (48 UE OD + CO Us %H) + CO 1H 54) + CO Ue ) + (9 LHL) + > gi 9) +O uO) +4 Ue) + CO UL OIE = UO +98 +H +9) ys 499 +59 + 91 = CA YA) = *p s}eqi0 20\n99I0W asp ooss4g fo 300aPL V9A Textbook of Physical Chemistry ‘blem 5.21.2 tution 10 sets of 2p, tals ducible presentations This gives? -1=0 =) zat] Substiu in secular equation along with nomalizatin of MO, we ge Eye atBi C= C= WE Fyea-f GaGa For x=-1, For x=1, Hence, the molecular FcBe ar Yee h-m ha) ForEjea~B Firkearf Wye ForRy= 0-8 B= LO -+6) ‘Work out the Hickel x molecular orbitals along with their energies fr tivinylmethyt H=CH); ical wivinylmethy belongs to the point roup Diy, The numbering cf atoms is ach of the seven carbon atoms contributes one 2p, orbital towards *-nolecular otbitals. These orbitals may be classified into thre sets—the orbitals in one set are not interchanged with any ofthe orbital inthe other sets under the symmetry ‘operations of the point group Day. The thre sets ae as follows. ‘Set 1 Carbon atoms 1, 2 and 3 Set2 Carbo Set3 Carbo ‘These three sets may bec [Based on the 2p, ori Irreducible Generation of SALC's A Symmetry E Symmetry Motecular Symmetry and ls Applications 651 involving 2p, orbitals which form the bases of above irreducible representations may be generated by considering the symmetry operations of the 10up Cy. We ignoce multiplication fctors as these are ascertained by normalization of SALC! set Sat Stl Paine meen ie Vie ttentes Fei 8+ 264+ 06 =O t ht op The SALC's 4 and ys may be combined so as to give SALC’s involving rel coefficients, Vo= Vit WE=28, 4 (64 En +(e ODD, = 26, +2005 ORB) 19+ 63) = 28-0 ain where €= exp(2ni/3) % = 2 sin(20/3) (4 ~ $5) = VB ~ $5)-» do 0 0 gd a-> 0 0 os ome al fo 0 @ a-a 198 2m 9 9 % Aq poosoy Sy 69 Fy aBunyo om no BUULUED w-» 0 d@ 0 pe oP ¢ 0 4-2 0 0 ¢ 0 a2 let Me Set oe| 2H a2" HH oa ane ae sre milter |e aH cy es a8 7%, spengHo synoojouN IO ge-o=% WAHL Cosme rleay tero-y WE eer Lesys ley, wa WE +H HERA “sont Summon an a8 pep+p ou Ws BuoT 959, 1 voyssoudyo uope 0=G-m9+ (deh) 0= (ie) +@-2¥+9'9 0-9 +@-2)9 se suoenba [0098 34, dew =] pur fetoatg ='z ont oso Zerpme-ar ax 31 =x (E=g)e say d [reg ar ame only fos la~> dgy eosldp go g og a ssuooog wweuRaorep seins oy “5248 Epi, = C9 Us 8) =A UT) = dep=8H="H io ony = iy £59. suomon dy 54 pu ayounats smoej0y9 L98 Steyai0 2eInooIOW ts v dsp = +d +9) sos coment = 6 ups co + v¥0L = 6A WIA) = Hr =w+n+n)i= vewrn int (9 HT) + Ug) + 06 UAT ONIE = 0 +5870) wn 08-450 + SE = GA tH) =H d=" =" o= wou 66 4% + OSL = Gn ELA) = d= G>g+oe= 0 Ug) + (O UYU") + C8 UA TONE = OO +59 + 99) +89 + OTE = CA A) = pewsnemi= 168 Wg ) + C0 UH) + (8 € ‘ants C8 e'OIUT CO HTN ECA) =H 2H Me | peices nce fey tw a anny om, seep smo mp 30 thy +1889 4559 + PAD =O% FAS + 5AD 4 Maly =F somounass aeudaxdde Jo 5. Suu 9 pourago am SEH s[nofou LL cto me O-4-¥0L =% evs (9-2 25h poe -9-40% =A mS T¥S ponqeanou au, ory srenai0 seIns=10WN seus! se n09}08, yo vonBuuiod assy porssyg fo 300021 V 2954 A.Textbook of Physical Chemistry ‘oblem 5.21.3 ution S214 Analyt feat sducible Presentations The above secular determinant lead tthe Yog2 Ce + Coe Yoo Cs + Gi¥h For both these combinations, the secular determinant is Pao eine Opening the secular determinant, we get Pe1=0 = re-I and ral ing combinations. These give E20+f and B= a-B B= a+P and By=a~ Sulstuting these inthe Secular equation Cy(a~ + GB =0 for Csla~ B) ++ Cyf'= 0) along with the nomaaizaion expression C2 4-C£= I (or C24 C31) sive the following reals Fe Tp Oh--W4 Ohh Bears Brash 2-6 Wi Bozo B The reducible presentation basa om the thee p, ocala Glee G % 6, af EG oe ia omer ‘The reduction of reducible represetation gives ~ X0,) 146+ UG) 2464) Formation of SALC's Formation of Molecular Orbitals Molecular Symmetry and Its Applications 655 Hence Ty Ay +28, The ase of projection pe } + 25,665) {eA} Ha) + D9) 6-69 4) Wha) + 9) CUAL Wh O01 = fer n= 26 Ja-e sp] x A tan fic se ia [tad nso te n9 Thisgies 2220 ce xe eh For xs V2, Ej=a+ 26 and for ref, E=a-vip5 1509» se 2o}o94 snp eps woRAUEsaAdDY afqzoapoR ‘uoreuuiojap s9o8vapin yonya gy ye yates om posa 190A a 9509 a ‘se sop poog ay afuryo Jo sua ut pascjeue oq Aom suoneg SuRMO}SP-ofUy ‘Seansodsas %q pur *y suowenasaidan ‘ajqjnpen yun suoneaqta Suyorans-puog 0 Suojeq woHEAGH Jo SopOU omy ‘SMU, tg ety =" aouay an Sueyaran (19 pu 9 ‘wea 10q yoea ZuneToosse 4 paesyeus oq eur SUonEIGE SumIDIONS-PuOK ‘safe puog pu sua, pg pure 'soyemps009 Teer wonzugia jo sopow suaiagpp 1 pamngem aq Aow suo! soBueqp Suygonut sudo 2809 24, (cuopeiuesaday¢ 30 01 ®) NSM soup (svoruosada!¢ 30 (201 ®) (cuonensoxia ¢ yo jo 8) tyeleeta= "a Weta lg= ey pagan 5 Joa} sae HN OLY (ssonewosadas 6 J0 ©) fact lace ty tye =" anny 24 “(L91'S 3) ntee poonpap sy ‘suonout reuoesgls 0} sBuo}aq (9-NE =) eam GORY Jo wopaasy 30 s30x80p (ve =) 2U1U Jo ea w soy ("2 dos yuIOd) ona Ire “qnoojou ay Jo suonow puoneagts an 0 puodsauos suonswosandes 2 2 -Potofap a4" aygN sBIEMYD ap WON} POLED oa pue [RUORE|SUEN Jo suonmuasasdes 9}q!oNpassT “OsOKN ‘uoag suotruasaidos91q1onpaus ont posyoso fs, POULT s1 oT YoeEOH ‘aypeun sian zejoxpuadied Kenna ann 9g wo pose suoneruassxdas qa!onpoy ‘Fumoroy ap wr poquesp se Apsompur pou ‘am soseq agp uo} suonoW YeuonEIgI YoTYN Joy SUonEIosader2fQIoNpau! oN 159 swoymoyddy 04 pun Kusruaets sopra2q0H suonesaip Bupwioeg-a16uy suonesqia Sujyorens-puog ayna31on, 2018), 40 ojdwexg suonoy feuonesaia yo suonmquosaidoy ‘iqronpeum, | “atreojou 8 yo soj8ue puog pre sus, ‘puog u soBueyp Sumosando1 soy yuuro2e|dsp[eUTU Jo SUD) UL POqUESSP 29 120} S-NE) Wopealy Jo s2eiBop SuruTeuan ay, onOW! pouonDsgyy ‘jneajour » Jo vonous feuortox an aquasap wopoo4s Jo soaiZop ¢ pur ajnsojout Jeu ym FeUITUON Y3Of Saxe dan ap FUE s829]oU Buypopxo) soxe om ap Bue 1008 24 eD WHOp2RY Jo saxB9p I topoay Jo ssafap 30 woot Jo refs oun unoure fue fq Are ue ssupuoduioo asatp yo auo Xue 20u1g“SaBUIpIOC® AE Jo TED ¥ "| OIE Y>RD 30} saqpurpioos a Surso0ds £ paquosop 99 we swidR Wy Jo BunstsUD9 warsKs Vy wopeery 10 soaiBog SNOLLOW TVNOLLVHAIA 4O SNOLIVINASSdaY TTEIONGaUUI zz's =I +9-0-n1e= a= [9 +0-0-B1t 09-9) Pn WE = 6A rn} 0194 yo stows oq, dyp-emta Hep ental all a ee en ee dy vo='a oro ee otal sal or BhaD-='9 dy-wate piso=9 dy ton'y 9) wordt woneasanou ok S-n'9. wim yyp-v=ty amo 108 om uqN syRsOU Jo (f= 219 whan Yyrtostg my 0= 9-H) +H '9 =" +a-"H) 9 axe suena 028 Aasrucyg porstyg fo yooqnal ¥ 959588 A Texbook of Physical Chemistry Example of NH, Molecule Jond-Stretching Vibrations. xample of CH, lolecule 0, Sy | Ge aM 440) ao Tag] 1 1 11 | teeach opis boad gis ‘sie i i These characters are hose othe A inedible representation, This ao follows fromthe sxesion Tg Pages Ammonia (pia gro Cy) has ttl of eve ( 3 N= 4) dees af which six (2 3N-6) belongs to vibvationd motions. As dete (645.162), we be Typ Z3A, + ALA From the charter table of Ce find that Tea 2 E+ Ay Tooeta {etal of 12 representations) Hence Py =P ~ Frau Po = 2A, +28 (tol of 6 representations) mn for which changes in bond-stetching vectors fort the Reducible represent bases is LN ‘This is resolved as Tras = Ai +E Commen: interchanges no bond vet and Cj change alte tre vet and each of thee 0 cpecation le one bond unsifted (4 total of 3 representations) “Thee arte angl-foming vectors 6, and 8, Based on het, the reduce repesenition i £26, 44] Conners A, Tan|3 0 en | oa (4 total of 3 representations) ‘Methane (point group T,) has a total of fitted (= 3N) degrees of freedom of Wich nine (= 3N-6) belong {0 vibrational motions. As deduced earlier (Bq, $.16.3), We have T Ay FEST 437, r 1a of 15 representations) Bond-Stretching Vibrations ‘Angle-Deforming Vibrations Molecular Symmetry and Its Applications 659 From the character table of Ty we have Tas = Te (total of 3 representations) Te=Ty (ato of 3 representations) Hence Typ =Tyy=Ty =A) + E421 (a to of 9 representations) Reducible representation for which changes in bond-stretching vectors form the bases is This is resolved as =A +E +T, (toa of six representations) epresentation IE we count the number of ins in Fan and Tyagi We find that there are ten (= 4+ 6) rprese there ae ten independent modes of vibraon-—one extra than the des of vibration. We find that Posen Vg = (As +7.) + (Ay ++) = n es) (Comparing this with eA +E +27, &) the spurious or redunday nether in Pau OF ‘denied based on the following fact ‘Thete are four bonds in CH, molecule and each ofthese can undergo a change in bond length independently of he others, But the six angles in CH, cannot be ot possible. Hence, the A, represenation in Fygy if fedundant. Thus, of tejspuadap ou 20 po ‘ajneqjor Jo vonewassudas 2jq}onpaat 40 t080q ayy uo} sereuIpIOGD sax 2H IP JF POAIDSGO St DOME uoHEZLEOd ON, a oan Jo susan un 94 Kou psBanut 2n0qe uipaf9 ap 2901s “ynoefou ¥ Jo aodsp-ouD9f@ aq 30 soesedo amy st Hf aay wees) spAawal ar se pouyop esSaqur wouous uonseuen yo azenbs snoop 51 /A ayes 8 01 A 01 ouossodaad 8 © utoyj uopisuen renreds v Jo SusuonuT ay, yo uouem9 NOWISNVUL T¥dLOaUS V 40 ALITIGVaOUd ONWOIGaHd e's suonesqin Bujwiojog-216uy aigionpey ‘2ueydseno2fou au) ut sie uoneazoop-ofBue Om a: aOU) tat ves oy paonpas st ta, 11 soseq ‘a uo} suor2en Bujyrans-puog wm} s98umyD YORE 30} uoRMUasaIdar aqA!ONpEy hace ty styes ype] sua, 199 suoymondty sy puw Kyruuts som22}09 se te 1p puy om “5 Jo ofge ssereys a wr, “art "ve+tac+ vee “(9's ba) seyp0» poonpap sy ay 9 ops op (We =) ana JO suey Jo oduiex3, sysue xs audoa'y ou “1 st vonqosa: si, 2 e o8uyp oy ciemronat® oS suonesain st io04 Buunojep-2}8be uo poseg wonewosaida 2jgonpa1 au, BuO}eG-O1BUY atten" Sn uonmos zo oy ie oo © suoneiain Sues 2 vo paseg wneosaNér ajginpe! au, BUNYoIeNNG-PUCE get WesMy MSY oH atten at en pug 2m age EB 90 ONE ast V+ Wyre Na 8 wom sth Jo ono a, 18 2p 01 SBUO AG (9 NE =) 6 WP JO WHPaRy J SIBEP (5 = Anos ued am on sBu0}09 QD 2Insojou Buy, ‘voneo}ap saa pus upg an220 y=] Su vg oq aap sopeuuoyop s9}2ue-puog Sand Jo sistsuoo 3 uomeiuasoxda 24, pafuoyo ame sooutr sueo Fy uonmruasaudas SUL 2e1p papayou0s 29 Kou pu0g uo “21 = pug Sind Jo jd Fo yo0RAL Y 999ametry action Rule for nan Spectra ay be stated as fllows. The direct product ofthe representations of the two states y; and y should coxespund to the iteducble representation to Which & 9, oF z, espe For the fundamental transition in the ith normal made of vibration, Eq, (5.23.2) takes the form Jvolisyrar Jostisivae [vol ‘where yp is the vibrational ground wave function and y, excited Wave function, It is known that, The vir round wave funet The symmetry pro 8 those of a tan wide he vibrational frst symmetc, ‘component ofthe dipole moment are the same tional vector along the same axis. ‘The symmetric properties of the first excited vibrational wave function are the same as those of ireducible representation of the normal me In order representa ‘Thus the essential criterion for observing fundament spectoscopy A fandamersal transition will be infrared ‘f the normal mode whi belongs to the same repr ‘one or several of the Cartesian le for Raman spectra is derived fem the integral (523.3) AT A RTT i : | ‘ Water Molecule ‘Ammonia Molecule Trans NF, Molecular Symmetry and Its Applications 663 6234) For vibrational transitions ay = ay (where J,j= xy or 2), and thus there are six dlistinct components. namely, 2, 0,2, ye and a These are transformed by the symmetry operations in the same way as 1%, y*2* ay, xz and ye. respectively The six’ Tunctions generate a reducible representation which can be resolved representations involving the above combination of coordinates. In onder that Eq. (5.23. is nonzero with any ofthe six components, we must have tive ifthe normal made involved belongs ‘one or more ofthe components ofthe ILLUSTRATIONS OF IR AND RAMAN SPECTRA Water belongs tothe point group Ca, From is character table, we find that active in both infrared and iso active in both inffared and Raman spectra. ble, We find that ed ‘Ammonia belongs tothe point group Cy. From its chars ive in both Stretching vibration E includes x od and Raman spectra xc and yz. Thus, itis active in both jon vibrations also belong to A and E representations and thus bath ‘active in both infrared and Raman spect Trans N-F, belongs to the point group Cy Prom its character table, we find that Swetching vibrations A, includes 2%, y* and iy. Thus, these modes inactive and Raman active Bending mode A, i ‘Thus, this mode is infrared active and Raman1d oy8ue we &q sive? xp noge 2yns2fou a ‘Suey vo pasia uoprsasaxds ojqmanpar ai ‘ste- tse See na9fou! a SUP, *q dros 29 01 80015011 ‘cpus Jo ana0 yp 2qnoqou eau & st (H—I=I—H) MEH} aUe|AEDE KL, eanot nour 30 51280 yp aU ota, oe Jo suonewsaxda2IsApaA HY MOON 1 worsnjoxo emu Jo aj ay, 2noefou SuneuTKSONIUED F a|NoeIOU £99 HLL {1 woprwasandar 8 ‘Sx pur 2x suonewasandar ajg.onpaus Boippe £q paurrgo st Yo jeutau ayy or puodsauio suoneagea Suppuag a4, suoweaquaameaua8ap-Siqn Sqsyouunds Kye st yoy Jo O40 "suonesgE o1eoUDSp-UOU OM) Te oe OF 1B yosondos Butno1fo} oun Bupppe Kq pourergo st 8% ew seanas clo ojqesoroesey> a yo wonsodsuy m4 CL [Se Ore Fee Oe a] are My sioroeseyp ay tustuste= asoper s | Mae" ex 7 one 1) an mi 502 2 zo 502 2 md 1 T= Oe F ei pay 2m yo age Jovoeyp om wos 599 suommon day 51 pun Keruauts soyromop Uuopnjog rezg wojqoig “00 20000 wn ain faye 3100 poe samgync scat pu 30 Wea jpauysun SuEWar sued a sed S00 amqu0o ora8- +H) & £ \Omozene 6 4 oyustn jo-oN ‘jue we kg eonpal ap ‘sr? eso we BUDyR, STINOTION UVANN V 4O SOW TWNOLLVHAIA 40 SISATYNY Pup sano pasnifin st uonouqi axxoe-seuey ou 2pDoqoMs opuimunutsous29 B up ‘moog Se pores 3p woysnpx9 m0} 3 1 umoury 99H ANE AL, suormuasoxdasn 0) SuSuofoq sopou jeuonesq 1 trjseue senfoau pur apesatun st weunoun 2fod on 20015 yp yong worszo4ur uo uss oBueyo 7 puw PUL ‘anne uewey pee ganceut yy s1 vonewosaidas hy Jo uoneaqis Bumrans ato 30 ajduiex Su;puog aut ew puy 2m ag saDEIP SH Wass Py does! ap 0 suo ANIA eyNDoJOW OURLAOL ussruoye pore fo Youre, V- +9Molecular Symmetry and Its Applications 667 6 A Textbook of Physical Chemistry Symmetry and Its Appl ILLUSTRATIONS OF ELECTRONIC TRANSITIONS nit 8) ce +0 0 ° ‘The electoni transitions in an atom follow the following two selection res. 40 0 ° LaPorte’s rule Bach component of dipole moment operator has odd (ungersde) parity. In order to obtain an even (gerade) parity, the direct product of. the representations of the initial and final wave funct From the character table of Dig, we find representing translational an roa This fact is known as LaPorte's rule which may The electronic transition between states of the same party are forbidden. ‘The characters of Pyy are E2649) uy 12849) oy Al=¢ L, where 1 is azimuthal quantam number. Telnet] 34 40089 1 Spin selection rule Since the dipole tomcat operator does not involve spin, we a) can integrate sin coiaponents of wave faetons separately, ino Inspection ofthe character table of Dug reveals that I'yis obtained by adding the ‘ale, the electron in bth the ial and following representations . vane : Sane si. Thus, the spin selection rei Electronic ‘While predicting the feast of electronic transitions a Transitions in a Moecule 0 2 2089 : For a doubly-oceupied 2 dep 0.2 tee ly-occupi ° 7 { bial, the diect product ofthe stme two rep 8 always yi ‘There ae three non-degenerate vibrations, two of which ae totally symmetric and H symmetric representation and thus maybe ignored in evluatng the ect pot 8 pair of two doubly-degenerate vibrations. | ofthe sate ofthe molecule Electronic ‘The ground electronic state of wate! (point group: Cis ible representation based onthe bond-stetching vectors 2 Reducible representation based onthe bond -stetching vect Sn E219) ei Water a cRacenen ian 7 : 1s sumametry is Ay as it involves doubly occupied molecular obits “The two electronic excited states of the moleciles areas follows. which is obtined by adding ireducible representations Zp Ef and Ey ‘The bending vibrations correspond to the remsining representations Th, snd Ty re and Raman active. These corespond f0 symmetrical stretching modes which do not involve change in dipole momeat. 12} is IR active and Raman inactive. This corresponds to ¥unsymmetrical stretching mode which involves change in dipole moment component: A, xB, component: Ay x By x By = zcomponent:. Aj x Ay x B, 1B) = ‘hs wbetoe odes ivave symmetrical bending which do no involve change ingle-electron obi, lowercase Mulliken symbol i wsed, The symmetty of lecroniéstue ofthe molecule i represented by a capt ler and Raman inactive.jo a00 sey susan "a x My sous Rags ky sty= Maxty +My xty, Cre tye By xtiy = fq ataxnaxty Req a Mtg x Mg xy snowodeo k pun x won fo Mgatigx ty xtly vero | a= "ax ey xty Gomis | "q="gx"y xy snuouodwoo-2 sonpoxd yoamp Suyxotoy am antoamy stexaray yuausous w =m oxox a 1 pea "20 on} Mo wosyuouDe uo 0 uonowesd oy ‘aosue wapprqio st sty pue eq «Mg uonysuen aif “FAOHOH 51 sue anfon Ms 2432099 Jo mnsnoads ouanDafa 2H, Ay kaaaraks tl) 0) wazvoq Jo amis puna atp‘Suonsa}9-2 9 SOpIUOD 2432009 aM SUIS dy spo Kuzueus somo2q0H we-vaty pm f-oatgnty fro=G=49 hsn='5 soos sare sx8su9 9, A syou nage 3 ‘atssaxdxo 249 Bus Aq ano paxpom jaa a ‘suonutvoxde (axoRH pu 0-59 479-4 9-H = Pans 6-419 -E = crap, 0-9-2 -# —"2) (0-9 -% +74) 00-9 2-9-4 +4 o: 4% 14 rT euszua ‘motto 9 ‘uy suopysues ‘re sou, “suazH9g Jo sTERHO seNASFOUEAL ay no FORNOH ANY 26 “61'6 99S Uf ‘21039291 woppronj ae soonpuen {878 my ned puRA anOgE Oy WOH MoMA) wov0dwoo2 “2 y uoneyuasaaday ounaumurds ATpeI01 e anfoutswsuodnood pera 2am | "Y= "ga xY_ waved soopssen eq pur *q->%e 0) soto sae stonysuen 2420} es fqu yo.NU! LONER o szuOwID a, nq = fax te suns coe ty atete oreumns (%) Ay = fq x%q cAnounks, Ga) C2) tq" serous ay 0) ‘iso se a8 ajeojoU a Jo ste paste awa 39} 24 fe comms 000) mg Jo aes oy puna 3, sioodoo2 -moduoo :nauoduos omsuaay 'q 979 asrucyg wosiyg fo wORRL V80 A Taxibook of Physical Chemistry 24 CORRELATION DIAGRAMS FOR A o10N IN AN OCTAHEDRAL AND TETRAHEDRAL ENVIRONMENTS ‘The number of ways of asigning two'elecrons (N= 2) amongst ten spin orbitals Ge itals is given by to! = OL as 4.1 m= 241) ‘These fonty five configurations along with thei M; and M, values are listed in Table 5241 ‘The assignment of tems symbols goes a8 Fallows = 4 and the nine pernitted values , = 3 and — 4 ‘The maximum value of M, associated with fj = 4is 0. This implies that $= 0. ‘Thus the spin multiplicity is 25 + 1=2« 0+ 1 = 1 of Mare+ 443,42, ‘There are thus nine configurations for L= 4 and $= 0 state, These may be represented by the configurations, 1,3, 5, 7,9, 29, 35, 2 and 45, The value of J= L+ S= 4404 “The symbol for L = 4 is G. ence, the tem symbol for the above nine configurations for L= 4 and 5 = 0 state i "Gy + In the remaining conf the that L= 3 andthe seven permitted valu 3 ‘Associated with Mj = +3, the maximum value of M, = + 1. This implies $= 1 fand the permitted Values of Mare + 1,0 and ~ 1. (Le. the spin multiplicity is W4l22x1+1=3) “Thus, with cach of seven values of iy there are tree values of, Hence, there area total of twenty one configuiations associated with Z = 3 and $ = I stat. ‘These may be represented by the configurations 9, 20,26, 21, 22, 28, 23, 24, 30, 34, 38, 39,41, 43 and 44. ‘The symbol for L = 3 is F Hence, the term symbol f L+S,L+5~ for L= 3 and $= I state are =3and S= ives J , ana *F, ‘The next maximum value of M,= +2. This implies L = 2 and the permitted values of Mf ae + 2, #1, 0, T and = 2. R, The permitted values of J are Molecular Symmetry and its Applications 671 Table5.24.1. Forty Five Electronic Configurations for d? lon origin -,_M,_[ 3K | Configuration, Ml, [SN] Coiguraion iM, +40 [6 oo [al 4m 0 0 wo ja oat fal ga nd aso [as +20 | 3] 4a, -1 0 v1 las trot | 3th gay 2 at 20 | m0 +1 0 | 3s! 4a, -2 0 soa fat o 1 | 36} ja, -1 0 +10 |x oo Jarl wa os fa} as -1 1 [a8] ma, -2 0 oo fm] ade -1 0 fa] Gay 2 ot +30 fas] diy et 0 fa} gay -2 0 set fas] aud vt fat] aa, -3 orale fava fae aa col ot lfre|| a 9) vot fa] aga, oo -1 Jal aya, -3.0 sto |} air -1 0 fm] aya, -3 -1 erie lor | ela ance tne <4 0 , Sand 2. Thus, the term symbols “The maximum value of M, associated with M;= + 2s 0. The spin multiplicity is2841=2x041=1 “There are th represented as e configurations for L = 2 and $ = 0 state, These-may be ‘The term symbol of L= 2 is D. The permitted value of Jis L+ $= 2, Hence, the term symbol for L = 2 and $= 0 state is "Dy ‘maximum value of M, = + 1. This implies L = 1 and the permitted cof Mf are + 1, O and ~ 1 ‘The maximum valve of M, associated with Mj = values of, are + 1,0 and ~1 (ie. the spin mu =3, For each of the three values of M, there are dee values of M,. ence, there ate nine configurations associated with L = 1 and = l. These may be represented by the configurations 6, 25, 15, 8, 27, 17, 32, 33 and 37. is 1. Thus, the permitted icty is 254 1= 2x11Gro ‘uns ap “see wy, en pg 2m orgs soroemey om WOH turunts 9 "308 aesouedep iqnop e pue % ‘as oiezoua¥op syden x on nds asa, Jo uopeyuosaudey -seusunXs expoqeo jo oun sin 2pun epuagep Bu ous SINO ‘eM, = NBUNUEABENG ows 8 + ODE + OT 9+ XSITE =" Bm '5{ wopmmesanda ajgonpar om "ua, 1a Ee TE coy pm + BE BB on = Com oH sores oro . putt 2+ Geto + og? =O ‘St xuneu uonewoysuen om Jo remy aq, £19 swomvonddy iy puo Ciounats apmompopy T= pu ~'0°T +z + =m TEND Pog {6q ont 519 donoany ap uessuco vonrzeuuou amp apse BuNeT - {0 dos? yuo 2m 104 uonemasendt aatonpas _Josaj9emy> ap aujurap 0} pasopisuos 2401 so spas g woroun a 009}, ‘pez om noqe wormot tp Sump pau st ave oq cous soeA g WORN ap (1) pur “(gonmos ain Suznp aueysu09 surat ‘219 anoge 30 Peto sf uo! *o'o'tma se poosaaas sno we ens juosqns a1 Fuippe uo pur © dsoxqns jevonro1 qwowuor wo toyenseedasqjoope jo aserep =) reipott Sp yowenemmreis; —— UeULSL us ance our, HO BUN (res) 8s, paw “a, dy Sd, Fy ae vontinayuoo zp 2} soqeugs sa 9s, 10= § por o= 7 20} yoquss ur (5+7=)0=/ 30 anyen ay ‘$507 mp yoquss ws 94, Tete ox cet +sc st huondomma ws a, o=spmg=7 somdun sma, (0 =" per 0 = 7 YoY 105 TE St WoReMMBLyuoo ZuruREUIES KUO IHL, + de poe Na jae [= § pue 1 ="7 20) sjoquss we ap '2uH "0 PUE I "91'S" “P= 9 + 7'S +7 200 / Jo sanyen ponuad au ‘q St | = 7 205 poquads maser OL: usury porsyg fo yoo9ny14. A Textbook of Physical Chemistry eg orbitals are, The dy and dy» ave lobes long th san yy id have lbs mie way betnen to invote ats eapestvely Wha egal charged pad Anpronches cena on sing the aes, tre teers fe the ats (iz. dy and o> 9) mote ant donno eee ce th anes (ey dy and). Cosequety.nhe osha eae ae ls ge ale a shown in Fig 5.261 The opting te weighted average such thatthe tl energy of d orbs Inthe ached cavrenmeat ean constant fn SSSI) Inthe limit ofan extremely large sping of d sbitals interactions between ce following configurations ich occurs when the the surrounding ligands are strong), the visualised, *+ Configuration, Both the leas occupy testable etal. The dtect Product oft ty and the itreducible epresentations contained in tare shown, in Table 524.2, Table 5242 Ireduelble Representations contained in , Configuration 7 2 Merete le ‘Te cary I represents imeducble representation tp It epeseats direct potst and ‘epics inedible representations in the diet prod ‘epic iedctleepesentaons im the diet predict, * Configuration fe, Each of the orbitals band e, cont izect product ty % ey and the ireducible representations shown in Table 8.24.8 ined in it are y Molecular Symmeiry and lis Applications 675 Table 5.24.3 reducible Representations contained in tye, Configuration + Configuration ej Both the elecrons are excited toe, orbitals. The dicect product of e, > eg and the ieduible representations contsied init are shown, in Table 5.244 Table 5.24.4 trreducible Representations cont ine Coniguration sresents te edible representation, I represents det product and It -peesnts he ieducible representations inthe direct prodect Splitting of the The spliting of SP, .. tems of an i the influence ofan octahedral environment solving more than one eletron under 10 E, and Ty, repre the octahedral environment: Following the same procedure, the orbitals can be worked out. Fors p, f and g axbitals, r Splitting of $ Term Since s orbital has a spherical 5 ‘representation based ons orbital ‘operations. Hence, the term S belongs t A. representation Splitting of PTerm For porbials I= |The character of rotational opecstion as given by Ea. (5.245) sia : 2) ~ “sio(a2)(SQ > pa > Gada > (aa > (aa ep panos 13 Kenuaansd poroidep ave sy8109 40 sapio Butseazut yp (2 42'S "EAD sua YOL-20y 1 Yo] awa aM UO © ‘Suynotog a wt paquosep se whe 9q fous wouuonaus jexpoqe}e we u} uot 2 ¥ Jo} weep uoR=uI» ay, vdpgou nds owes ayy oney uo seaned » wos; pans ‘ue suds vane amy tab Kpoan ioes=Ta! OU Soop joUMUONAND TeORUDYD ay, wuos}va eaponroo we uy suopewuasoudoy pus My, fy Ty ony sds g wim am, gn 2 2p “uorsDAuY 0 wana ame sTENGHO B 1970 dos xp 3o gen sazenyo ayy wor DE 103 yoyo. sy uonewasordor a1qknpay aU, .05=2 worst SO. a 0 wonmos 9 Seas Ot amor = SE SGT =D wonties? I= Sous * organ "@% aT = m0: Fo ancy 94 “90001 U9 suoyoonday sy pu Kyou syro=,0p) wei6819 ‘wone}01109 yo uonanssuey Ayoudeinvy ids BuluBissy re ‘quan st wofado jauonmnes jo arerey> a, a uoat8 st suonesedo fevonmos Jo SEIN ,“¢ =| “STENGIO 330g ‘uourvostauo ferpoyeso s9pun uorreosaxdar {2P Y0 q wae om ‘2ouap “h vorErUecosdor 2 ‘onmasaud anoge ai em put ax ‘0 dnos 1-0 0608 coeous * uno}. 9 40 Bupe 0 J HoH 30} uoneasaaTas jglonpas 4, y 060 wotmas"y t= wore ost =” wonmes’5 2a 2m 2002 cms _ copa = wey 4 0 Bund 01 suojoq woresnyuo> ‘qn 01 spuodsa1i0> qe sIORZEYD aM OA 1s | ox 9 oe Qo 9 a | Oo sq ag any sqegH0 d yon Jo UoReaasandas a:ONpos BL, spas ‘sere opus pares 06.05 eas ~ Loic ~ ° Y oy Y (06=2 oH? ou1=2 — vonmety yy —> iy, "a ° soy 50 $008 woneusisep ay souopy Angus Soyo yy Ay ams a beaux ptm suoreussaides anoj Jo TIO) ® Ma syenmio wos Me egy owes so pans seapon asp 2a 0 yo wns ony 5008 7 onpoud mp au iq 8g +e 0 ano sa08 quo 2S Saety Se ny va suoneu uy om qo AaomU am FuBDKO] UO “suoRRNDS spray £9 [oh9] 94, wowDumSifuoa Fy wosf Basun sims — ‘amquse foe ynpen puts 29 uo pue (Ss ae sore: BURN TY bars: yrm-d din use a SQ 0 SO way Btpuosep wo "ody ‘ois pus ays yao fquo st ae sours X 1D y=] SL 1 tendo Koesuatap yy 01 spe #8, SOU 199 suouvonday 9 pu uouauss s0r21OH) iin Sst na annette Taras “ayye aria fattae'y tare "ay peta, =Fax oe j= @lexiare tavaey "L tarty ‘a yy. "> ct ‘suoyeaoysuen Zupnoroy tp puy am % dnosfans ap funsajog 30 51 vonpuna sup But dross a, reas samoq Jo dross req apo ax uo paseg st pou Sr, aU ‘ureysoey 2g eo oxen 5 getmvonau9 ip yw UO! ay Jo suoRE=.N Furs 4p ow 20 poe 2 span, Kou aan wou Buse snes amp Jo Adu Uns a, Anouuaks Supurssa¢ Jo pownont ou, arruoyy rooash $0 YOO, ¥ OB82. A Textbook of Physical Chemistry 1G ae Be tot 55 a, Under the influence of tetrahedral symmetry, d orbitals are n longer degenerate. ‘They split into «doubly degenerate set e and a triple degenerate sett as shown in Fig. 5.243. 2.5243. Pte of serps of dorian ‘trahdralgymmetry h-9 21,42, Goa sesti et, orrlation The coneation Fig. 5.244) diagram canbe compte by joi ‘gram left side (weak interacdon with toe of wong intention sdeerbed in te following, 1 in ' is joined with Ay yin bth A states onthe and 'E state in 'Disjoined with Estate ict in both state onthe right side. 4 Assigning T, states in et as" and 1G and °7 in ey with "Tin °F. Siialy 3, we join the states "Ty in ety with "Ty et, with "Ty in *F ‘+ Weare eft with 7, in P and "Tin 'G on the lft side and'T, and Tin on the right side. Thus, we joint" inP withT, int (establishing triple spin degeneracy in T) and 'Ty in 'G with Tin, establishing tiple spin deseneracy in) ‘This completes the corclation diagram (Fig. 5.24.4), tats in ea" and ‘Molecular Symmetry and Its Applications 683 symmetry operation ry elements and the associated mote elements the existence of C, and (Show tat he presence ofS, with x= even implies the existence of Cyy and centre of inversion, (8) Show that S, with n= odd generates 2 open 4, there is Canis perpendicular othe principal sion by 180° followed by reflection ina plane perpendicular to equivalent othe cone o‘nr nebo 1 suonenosaiden ‘ajtonpau wep OM JO sso BupuEdsaL JO NEnpOAT jo INS AHL, () ranap) aug pu 9 S290 JO Soe aa WMD se ous jpouyop xine x Jo tts 1 siounss jo sjnpaid Bao} eon EAM somado Ya HEU) Dx? (a Dx suopesdo a jo sonpoid Banoo} 20 “qaox8 aw sop pe ds Jo Suonmneradas evrruamp-2u0 amp da es “5 Boi8 nod si jo stopmiosandat euoseacap-ovo a dn ineou SH wow Inn jo a 2 poy “ s20008 yruomos a UO poHes Ey dos Od ‘9p yo suopwnoseadas etruatp ano nas fe2f0u OFH JO 2kumxa we BUERL “6t 21 oo 908 uo peg “> doi wrod “omnojou Of Jo ofdubxa ue Ror “Bt oi od oa 052 domes dnos® ay omnEHOD “Lt um ons ann tyes ne er ee) ‘pogo mpopuodind 9 pm € 2s ap a0 oes opps sxe) ota $99 suotonday 51 Pay xounuts sorns70N asnacye roysiya fo yours ¥_¥8986 A Textbook of Physical Chemistry Describe the Milliken symbols seco desigteineducbe representations, @) In the group Dy show that he ois sand dy belong ay: dap belongs toby es long 1 oy fe otelong 6 the operations of he group Dy and ten may be) (©) Io te group Da, show atthe itals 1nd dy belong; py belnge 33 eB, belong to es dy belong 1 e” and pp belongs Setup te poietionoertor B= 1 Ye CR Molecular Symmetry and ls Applications 6817 mo ving Is obials of hydrogen atoms and also for melecultoritals of BH molecle. involving Is orbital of bysopen atoms and of CH, motecue. 48, Setup character hls fr they tp of ork rom wo i ivoring ch element 6, = = Oxi). Wink: Fee Gyuse P= et and =~ 2) YB) = (VNB) = $h- B= a B v3) = (V2) (6-4 = a BI in the planar AB, and AB, molecules. cyclobutane. Determine its Aelocalization energy, charge densities and bond orders. 57. Work ou the molecular orbitals of rvnylmechyl radicalpor wu pop a Jo sco mp nT SHANE axojiae pgp esa nln an sR! SEPA a NO YON, “OL we, a dap - 2108 -Oyp 8-9 +1629 WIE «ea oa a 4 A pag te +zp 1849 -ozpy = gre lps = dye =3 ‘ a = osaya eng eo peas -OE = tA 1 8 poate 66) E oc eyes ' : as DE CtaA ‘ontie=s | Te 6 3 dep 0-908 -Oyp 6-16 ep OEE = (gna fap 19-900 10 orp 9-8 sy teif- eo 2 ge wee ee he fen ag fetes 0-0 18-0 Hatod aon ea Dag 1D OED HD Tae | eae i ae 4 a termes seam ee rare r%ew 2 2 2 | Ag25 aqeootow ayp yo sosoue aarp ue S129 my és | oe tot ta dy 8 geeweg ace 4 02 =a ‘size =3 | pb pb Da i er, | ewer De | a 4 er 5 wee 1 rifa 4 o aves toioily rey ar ‘aor amp yo suonoesern) Baons ap aon $0 pre % oe a] sm yn 9 ; ©) -meuwonnse pce wm ot 30 mip pM a AHHH HC) ern er WED, ° 1 ae eee ee Paar eale TPupoueao ve u vonemguc> p Jo suey oH sp Jo Funds ot 0 OH (A) 4 swonnguoo 4 (2) pu 3) %4 (2) at somesaxtssatoqpant op M0 7HOH (8) 9 Gras ra) eee repeyenas a) poe “opamoo we () uf sana wt ds MIO p NOH MEAT YD pea ‘eras | rola ‘wopesnSiguoo ,p aq 20 sloquits saul) xp ouREEAG “C9 ete ue i 1 ¥v ‘uoqsnyoxe TensnUs JO eu ap ANTS "7D [es als | ust po vpn ae ose IHS > AAPA a SHIN “19 snag "9 2UL *T » SARL, JAPEIENL Pas <[uouRMOD auto —_AAXANNY. ‘yen (e909 wonow euonent Jo sBojRTeaEdo a onsen aod 3 yea Sop 48 9 SBE estoy osiyy 0 00902 ¥_ 8890 A Textbook of Physical Chemistry ‘The, Groups ape ce oy Hi aa 1 4 rftooa ot afta 20, | 1 rane aR GRR) | yon Care i Oe) 2G 207 | 4 1 H ere yi aR, : a Bop 4 1 » } ° 0 Teriteey | Ga.x8 KLE Me % G 3G IY wfpo. ot Pene Mfrob ot or a at ew nya ab at oat eee Fla 1 a 2 oO Janeen) Ga Sal eed yn) ‘The Cy Groups BEG shed 00 | = afoot 2) Boe ain et et tee a at] aii a 1 a Jay |x ali a a ot fxm | x Sy] E20) | alto : Band alto R B{2 4 o (IRR) | Oa hGe7e) Molecuiar Syramesry and Us Applications 691 weneelo z vane eH »y RR] G7(loot eo Fr te took er Rot tty ror rh tot ay corpse | Grew] oe ne aloe oo a] ty ete ee 1 ty ee) Ge al Ra cfm lane | 0 eo tla « | a. tor 4] fe we Pewee i ples vwlor or 1 oy uly gkee 1 @ ma Mt H H Tor tor en 2 ec | yw) « ee ¥ ever £69 sumone sf pun Saxouas speo2topy com (Gr | oe vot yfr or r ear rorr3ote wey-p] ool o or too re Bie ote las pee nares [See SE Ge . rior oe ‘ Ror oF > ror 1 Dt 1 x fy roa re am \o bor re & a eo eee rororit t 7 wo WO sdooiy "a 98 a2 2 mre et { m3 208 2 ee et | at ee || Por bier rer tortie Ape or oR or oF pore oa t|y eR Lm e1 ees oe fe wm (DS Ph tier fy wnlay (7 ho ern on, ome | eelral| eects ere ot Ror oR Ik torr rit eéee| fr or tot ia eee Gaaena [Ss BS poo oT usar poossya fo o0areL Ve94 A Textbook of Physical Chemistry PRE R () (-¥,9) eR] Gard eae sx | €= exp(2ni3) torre R wre) BT LE | em | er oncere Molecular Symmetry and Its Applications 695 tle a 4d sq eS expai2) alia ova Parse rlt «6 @2-2-y, le oe ey) Ths 0 0 3 | eR R22 | mV Te] 8G 3 bo | re Pee is eee el 2 4 2 0 0 O2-P yy) nls 0 4 4 RAR, Pra eet eda liasa) 72) OLE 8G 3ceCd 66 664) aft oo Twi eayee aie ete el2 41 2 0 o 2-2-2 1/3 0 1 RyRy 1, [3 0 a rr ttt Payee o 0 @2-2-7,2-¥ a4 RR) toot Gere 9) tot o 6 401 o 1 1 Japadn 2m pue ors amjosge 81 U9 ‘aia, 430 eu HoE8 ey N01 240 SN ‘9 ung an Se sede 20 wT 200 Aq pares sin op -poed Buc} 082 0 gore yBnom Summ, vay ne mea an jo spear 24, ‘wore ger-wunysse> puna ap perp seotrueg soomsqn yo sou jommony amend x joy otueuspounoa, v7 axedwe wate ato . pooaoe oo, Sumter 30 o seu p80 ‘Given yun fo oy atta ‘SHUN 1S U1 SeRAUEND OFSeG UONES F1y aIaeL. FIV a1ged, uy poquasap ase sayy, sun 1g 0 sounuen aseq woKos av ata, suun is so}oe UOISIaAUOD PUE SHU, T.XIONSaaV aay oe a = soma 29Ur1 30) a pur 3 sda 2a, Kasrueyy porstyd fowouReLY 98 A Textbook of Physical Chemistry Units Derived from the Base SI Units ‘Shmbol and defiion Name of wie Angulc velocity bert = eye per second square mee ‘mete pe second radian per second cai mete mi Acelerion sme pec sure second Presa newton per gue mete ox pascal Condsiviy siemen s-a! ‘Magnetic fluid density esla T=Wbom*=Vsu* lec cptciance ——farad Feev" Magnes fax weber Wo-vs CGS Units visé-vie SI Units rere ee Pivial guy 008 wi ane Tame Sloe par ine a Angstron A Mas = tte ie Tine fond . os | ei " Tongeee ei {Ewe ok ey ease et Ghee eu Salas eaimeptee hea oo o Bec une ‘ A eet ns ANS nese Molecular Symmetry and Its Applications 699 Conversion of CGS Units to SI Units Deny Euan Length Angson,A 10 m= 10am= 10" pm ton, Vole live Foe dye Enon en al wv e021 103 Vince 584861 mot! Presse atmespbece sll (or Ton ae m Vucosty prise rohegertet Magne ux desity gauss wt (magnetic induction) * Symbols wed for factions and multiples are given in he next Table St Prefixes Fracion Prix __Symbol_——Malples——‘Profe—‘Smbol—_ ect 4 10 deca a w(22800 annsod ) (aon aasod ie iz rasan 8 ae dete Toytten te oust a9 s00= J ue us t s000 909% Cg" ws 900% g s00 (i-nyae Eegenan Ea gno0 a Gams Seg -mu grea Eg-mu Ls gusnus Spqendry yooxp pur suoyssardyg jwonewayyy}y aos I XIGNddd¥ agavzon2 1585 9 OT x 506 L667 3 p01» socua Om OL eb ZT, ow ) gue ea TH oT agama seg ao open ues yo uogeme00y com N6 Tas mam 7 srueicd aqui hig owes SERA a Aassnuayy pons fo 40092 VO1A Textbook of Physical Chemistry I [es tet ae eo max Tee cog Max = 5 58m (pose integet) jatatace Gand nines) Juvare afar [(P)fosoae Greek Alphabets: Sy Sa Name Roman ltalic |Roman Teale} Name Roman talic| Roman Italic Mae AA pw epee we 8 Bip eis = els & cae or rly 7[onem 0 of 0 0 ome at ta) prope ge | e min EF |e «|mo P Pip p mz 2|% ¢|sm 2 lo @ mo ala g(t oT Tle ¢ ten 9 | © 6 | Up vy vf[ vo me tr) sr lm 8 Ole tm ox K| x «far x xfa x une 4 ala afm oe ly ¥ mw om wi slow o o| o © Index Aetian group, $51 Atharmoniiy conan, 469 Antares vation, 468 Ancesls Zeeman effect, 116 ‘Azoboodng molecular atl, 235 Ansi Stokes Lines, 492 ‘Ansisymmetticsetching vibration, 420 Antisymmetis wave function, 45 Associated Laguerre equation, 85 Associ Laguee polyromit, 85 Aus of symmetry, 536 Ainuthl quasi ausber, 91 Balmer series, 19 Bases of repression, Bond order, 257,318, Boncag moteulse oral, 235 ors interpretation, 34 Bors Oppenheimer approximation, 221 Boros, 132 Carbocytic sytem, 621 CCeaue of invesioe, 580 Centre of symmetry, 540 fon ctabedeal environment, 679 fon in tated enionmen, 683 Broglie relation, 28, 157 Del sqused, 318p “aagesgn yo epoe asey 35 dros p10 wot onupin wn ‘yo wauneen OW OVI 92 “epnony atorptg Mt otsond some Oe “pe aeecosRg se “sqooqsaaomp eoneon0g 9% ‘soit2}0u surety se.seum.9g vez“ ove “iH ste 5h ‘wopmisgs aoe ne “noview eva 09 09 (2 pnouo wages 5 Hep eH soe Pu {rey “toaes aydecs auyssdg 22 "20 oxon wap ze “que 959. “woneey vas. “wotoou, 6 See “Pome aoueeg een) est “29020 up vonage peepung “veya suey ng ap “otter ead touIndex 707 Rebeanch, 483 st hy oi 6 dial distibaion function, 102 sp? hybrid oils, 278 i amas shit, «89 Space quemizaon of angular momentu, 78 Normalisation constant, 38 Photoelectric effect, 8 ster gfstor, 402 . | Redaciierepesentiions bated fexponeat, 125 ytd, 272 281 Symmecry adopted linear combinstion for ‘ammonia. 609 ei hyaide 604 Orgel agra, 612 Orthogonal. 35, Ortonormsl, 35 Onde of group 560 Rutherford model of a Symmetry element 536 Rydberg comtant, 1 Symmetris functions, 2 ‘Symmetry operations 536 Schonfies seston 536 ‘Orgs! diagram 679 Probabivy deny diribatons, 99 Point Group $82 Prob 396 vedap density, 223 Projtetion operat $97 Overlap imegal, 280, resonance spectrum of, Overtones, 471 Petraneh, 483, rotational energies, 68 Perturbation method, 124 tcaalional energies, 37 \ Phun series, 19 / Phosphorerctoce, 506 (Quanta numbers, 59 } 0 byeid ovis, 274999 se "pom to yuu or “ows srapaaiy any a, SU 'C¢ Rom woneura,