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 .. 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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