Group Theory and Chemistry David | M. Bishop Dover Publications, Inc. New YorkSEE GIADA Matersnan Internati Cori Conventions 8 The Lambe, en co ‘Tandon rat ‘Ts Dee i, aed a ated ed ‘recs Onan "Anew soclon ed Answer Te Sate Poems ‘Boveri Bat Sn Sec Minol, CY. Sat itary of Congres Coleen in Paitin Data Gay ary and emir Dai ido, echt ee corey tam Beha Snir, Pye on os Shee one FAW, DRC,[rm | ‘Tas book is written for chemistry studenta who wish to undertand tow group theory in sppled to chemical problams, Ussaly the mnjor bataclo chemist nda with the robject of this bok ix the mathe ‘mation whisk ie involve consequently, I have trod to apll out all {he releyant mathematic in some deta in appendiae to each ceptor ‘The book oan then be rad either ss an Sntroduetion, dealing with _gecral conenpta(gnorng the spponden) or ae a funy compretensive ‘ception of the subject (including the eppendion). The reedar ix ‘recommended to sn the book frst without the appendiens and the, "Phe eubject material ie wutabe for & wnior undengrdante course (rithout the appendices) or in 1 Inctree (with th appends). ‘The bet advo about reading « book of thin nature wae probably that given by Goorge Chryrtal in the preface to bis book Alger: Every mathemati! bok that is worth reading must tered "bckrae {int formar iT may ue the sxprenons T weald modly Lagrnge’t ‘vio itl dnd ay, "Ga om, bas chen rca to strengthen oat ‘Wien you come on hard or dear page, pat ove, ad some bck {ote aker you bare sown is inportatce found the ned fo fret Finally, a word of encouragement to thou who are ighteoed by smathemation ‘The tathemstes involved in setualy spplying, me ‘opposed to deriving, group theoretical formulae is quite tivial Tt {vols little more than adding and multipsing ein fact powible to make the applications, by filing in the nesomery forme ia = routine way, without even vadarwanding where the formulae have ome from I donot, however, advocsto tia practi, London DME. November 1072roe poten es ect eta ‘See nee Sa ceria ett SREWLoIn ST woe timetneo SCE oi pnp ee eg iat asa Ornate a FE as Sconce tae Gor BEd: Siam armies or‘Poe dagenlanton ofostr ho to fd th overs Ace, Bota Saath = bata s ‘nae 2 $3 Mie rpecmumenonegcaeee mABP REAR agent pong, ot 2 a te 1p REE met ees tomar, AS: Rah oe pense eo Pusitveesaee ste ih Ee ees Sees «, gn ne ri ‘Eqerens mpremetato aarp pao rprenains ‘Rosenstein gute Oy pe try it (Conknaios snd arene Lvl ad Ped setae AGS. Syeometry properim of polaraabity functions 18, Molec eh ry ‘sinne S 1: Orr nt va i yt ald hry mete Cote 127 Comtaten diagram Sel pen Rae ern ee an ar mbes for my alert tom or Hresecke dla (enn M029, ‘Goa vous of pout Srementeton fe pint pea telat areneng hate {5 mete Alene in eth row and ih clan of DR) 2 See oP do 1e projection spear E24 /Oy ‘he projection operatr $ DY(R "Oe ‘he mutex representing RSs the regular represetation I sg opera ft a ae of ofan gr ‘i jopeatioe of ha mth eee 3 pase roe ‘pute Taing She aninale songs of» oh ETERS ovo pains in det pdt reSymmetry 1 overpay language we wie the word nymmcry in oe of to ways snd conepondingly the Oxford Engh Dictionary gives the following tio deine (1) Mutual retin of th pars of somthing in mapec of magnitude sod position; tative meavutemant al arrangement of parla, broportion (2) Duo oF jst proportion; harmony of parte with each other and ‘the whol; fitting, regular or balanced arrangenent an relation DProportoned or wel balance. ‘Ti ft dainion of tho word has a more clei rng toi Yan below concept of benaty, for exarple Foe Bulwer wrote in 1680. "True and aativo basty conane inthe font composure and aymetee ofthe pets ofthe body Le x nonethelat interesting that whoa we {0 deeper into the scsi meaning of rymmetry we Snd that the deriving mathomation involved haw ieif m beauty std elegance ‘hich cold well be deneribed by the second deSniton Tints chapter we wil it look at eramty a soccurin overyday ‘oad then consider ite specie role in chomaitey. We wil od the ‘hapter by giving «historia! sketch ofthe development ofthe mathe. ‘matin which a uoed in making ve of metry in chemi. 1-2, Syme and ey ite ‘The ubiquitous sole of aymmetry in everyday Me has bean neatly summarized by James Newman inthe flowing ay Syometey etabliies »riicaloas apd wonders coulaalp teeweon structure of epace, vauc designs, quantum Diyns, scarab, Hower petals,cma ntfs pata, el drone ring, guia pins nM Hoosen nora, ane, the tory of in nok we find eountem exampios of symmetry and in Fig. 12. vrs show some rather beautifl examples from tho sal, vegetable, [od eral ingore, Extoroally, most animala ave. buster ‘ymaetry that into any they contain ange plone of syomcry wich TTptme Unset very ocuight ine lain pit of coneponding Pont, "This the mae thing ne ening tht tho pane divin he objec nto two parte which are mitror imager ofeach other In ig. 1-22 It toon thatthe fry leaf and int have, perpendicular tothe plane ofthe ‘eam, and thre planes of ayimnetty reapctiely.Aetaly, the ‘owt foquent nati of planes of ymmetey in omer ine. Anyone {ntertet in the predominance of bilateral xjmmetry athe sal trea, with it covllry of left ad ght handed, i ocommenced {oon The ambidentvas universe 2 tn the iin we lao notice that there it thon fold ans of symm, that is wo rotate tho Dower by Srft radian stout the ate eepedioular to he page and ranning ‘dba the centre ofthe flower, then we cannot tll that it bas been ‘moved. Sinilary, the lon eryral fn Pig 12.) Bae » aixfold axe of ‘ymmetey: a D/O rotation lanes it apparently wamnoved. Because of ite basic sethotic spel (regularity, pleasing pro: portions, parlodsity, harmonious arangesent) ayminery ia, since {in immemorial boon aned in art. Probably the fret example tid ‘aperenoe of the benuty of eytacety in playiog with s aledonsop. More eruite examen oocur in posty, fr example the abeke rhyming equencn in many poem architecture, for example the octagonal ‘ling in ly Cathie one Pig. 1-23) tou, porkapa te moat arte ‘hoof emmy in te ina to part pleco of music which i wometimen ‘Table Music for Two om 2 1804 tae sttsibutd to Monat} ove part bing simply the wpa down reon [€the other; conaequentiym single sopy of the vooe can be vend by both player (ooo Fig-12.4); and panting and dig, se for example ‘he apecinen of Bottish bookbinding shown in Fig 2.5. 5 Kesha Pens coe of Meares hse ‘ays en ps ahaa nn alt soy tea6 tymmeey (ne thing we notice a that al of ten example involee either © plane sn ex oro sone of symmetry, which in tum deine plane, = Tine ors point about which the objet i aymmetee, 12. Syme andshomisty ‘The involvement of symmetry in chomlotry has « log history ln 4p me. the Bovey of Pythagoras eld that earth had been produced {rota the rgular hexahedron or cabo re fom the regular ttrabedro, At from the rgolar octahedron, water from the replat iooebedroo, tid the Beevealy aphore from the roglar dodecahedron, Today, tho ‘Sersint Sntultively onen symmetry every time ho resognizor which ‘one in a moloate are equivalent, for example in pyrone i in eaey tne that there ae thro sets of equivalent hydrogen atoms, The ‘ppredaton of the numberof eqaivaaat atom i «molecu ade to the polity of determining the number of ebetitutod moles that"can exit eg, there are only three ponble monowtbetiated Pyrene. “Symtetry alo plays an important part fn the determination of the strvnize of molecule, Hee, great deal ofthe evidence comes from ‘he meararement of eqyatal stractaren,infrod sped, wey violet specten, dipole momenta, and opi seit, All of thac are proper ‘ike which depend on molecular symmetry. Tn connection with the ‘spectroscope evidence, ila ntareaing to noc that i the praace [ie tamour book on group theory, Wigner wits: hc iM, Lan) gto ao ihe dre a sponse of Laprs rion some of tart) andthe. qantom SEZs Tatte con apes thr caver tet te maton ta tse al rb of epeuctopy Sow fom he sym of te poh (Of course, the basis for our wnderstanding of molosslas structure (rather than simply lea detrnaton) tein quentom mechanics bd Smmery ‘therfore any cousideration of the role of symmetry in chemistry in Dusially« consideration oft role in quantute mechanic, The Ua ‘botwoen apmetry and quan mechani ia provided by that prt of mathematin known ox growp theory 14, tric teh ject known as group theory, We wil, however, now biy ai the history ofthis theory, 'No.ne prson waa reponse forthe gro Hea but the figure which looms Target lo tt of the man ‘who gave the concept ite name: ‘Brariate Gali (1 signidcant dacovein. He was born in T8LL at Bourg la Tene jurt ‘uta Para, und by the age of axtecn he hd oad ad dart ‘he works of the great mathumetiinea of iv day” However, despite hin genius or mathomatis, be fale twin the eatrance xatsnutione to the Hoole Polytachaigie which war in thew daye the Sects for Trench mathematicians. Finally, in 1590 he was otepte atthe Boole ‘Normal, only to be expelled the mune year for'a eewopeper letter ‘concerning th actions ofthe nebo distr daring tae July Reve ution, Galea had alwnge beens convinoedrepublias and bad a teong ‘uted for all forma of tyranny, 0 ew ot rorprining to fd that in 1691 be was area for proponing a toat which was interpreted 8 threat on the lf of King Loui Phlppe- Ho was a fiat scqutted but ‘hen, shorty aftervarda, ho was arreied agein snd senenood to ‘monthe in jll for Wegeliy wearing «uniform aod carrying weapons, ‘died on May tat 1882 when only 20 year ol rom wound wosieed ‘rom being shot inthe intestines daring = duel. The duel wee fought, Lnder «code of honour, over «‘eouats' but some hstrane bellows ‘it wae inntigned by an agent proweatur om the monarchies ide. The ight before the duel, Galois with forcbodings of ath wrote out for Doster notee concerning his most important dacovers, mich at ‘hat time had not been publ Hie total work ir lear tan ety ages "The concept of group had ben introduced by Galois in le work on ‘the theory of equations and this wae flowed up by Baron, Augustin {Louis Catchy’ (1788-1867) who went on to originate the thay of [ermtaton groupe. Other eely workers i group theoty wore, ARAE Cayley (18105) who deine tho general abstract group ne we now© Syme lkxow it and who atthe same time daveloped th theory of mates; ‘Camile Maris Honemond Jordan (0838-1088); Matas Sophaw Lie (1842-20) aod Ladwig Sylow (1882-101) "Por the chemist, however, the moet important part of group theory is representation theory. Thi theory aod the idea of group charactors ‘rer developed alm ale handey atthe turn of th contury Dy {ho German algebraet George Ferdinand. Frobenius (1848-1017) ‘Through a decade nearly every volume ofthe Berner Sitangberishte ‘tained one or other 0 bia heautifl papers on this ebject ‘One of the sao ppliatons of the theory of groupe wae in the sady of rgealatrcture and with the later dovlopment of X-ray ‘halya this pplication wan reviled and elaborated. Thin, however, Dpurdy u matter of geometrical slniScation and though woeful In ‘Mtuloguing pone typee of cxjtal, Ht hus no profound phyaoa ‘Seniteance. Of much tore importance le the work of Hermann, Weyl {ls80-1006) aad Ragone Peal Wigner (1902-) whois tho late twetion St thn ontary developed the eatonship between group theory ed Tis interning that Wey! had a dep aonvition that the harmony ‘of atte eould be expremed in mathematically Deautfl awe and an ‘utatanding characteristic of ie work was hn abiity to wntepreviouy Srclnfed wubjecta, He created a general thory of mate repre tation of continous groups and dincovered that many of ‘agularition of quantam mechani could be bet understood by means ‘Wigner’ greatest contribution was the application of group theory to stomie and nuclear probloma; in 1963 he sbared the Nobel Prize fo Dyin wth J.D. Jensen and MG. Mayer. "Pnalyattntion io drawn to « gerioal paper on the aplication of ‘esp theory to prob concoming the natare of erystln which wae Dublited in 1928 by another Nobel Prize winner, he Carman phytic Hane Albrecht Bethe (1000). fe wil eonclade thie chapter by noting that iti one of the moet cxtreordinary things in wience tet something oa simple sid abutmct tithe theory of groups should be ao usaf in the practical and treryay problem oft chemist and i pethape worth quoting here ‘the English mathematician and phloropher, A. N. Whitehead (1881— 1047 who mid ‘Tes no persdox Wat In out Tost theoretical moods ‘wey be nears our mont praca! applications TA. capen Pt op i340 0, te el Fr Atte an in rT 2 Symmotry operations | "Tax porpone of tha book to show how the consideration of molecu symmetry cam cut short lt ofthe work involved inthe guano ‘mechanical treatment of molecules OF sours, all the problem we ‘rl be consored with ood be milved By bate fore but the nae of "ymmetry is both more expeditions and more elegant. For example, ‘then we come to consider Haske! molecular orbital tory for the Trivinylmethst reel, we will fd that if we take account of th ‘moleule's ymmetry, we can reduce the problem ef eclving © 7>7 determinant equation to the nach easier one of tleing one 39 and ‘oo 2? determinant equations and this leads to baving one cube felve” Symmetry wil alo allow ismmodintly to obtain tefl qualitative lnfortation about the properie of molecules from which ‘heir ateuctare can be predicted; for example, we wil be able to podiet_ the erences ia Un intered and tama spectre of methune and ‘monodeuteromethane and thereby distinguish beoreen the owever, to atart with we must got clea Wen what ite we mean by theoymmetey ofa mona In theft place eat ooeslersion a te atrangement of the atoms or, more precinly,the ne) hair ‘qi pontions, Now, when we lok st diflecat nuclear acrange= ‘ments, xabriour that we requir a uch mote pre and wcente ‘otnition ot eymmety than any of thowe given proviouly in Chapter {or clearly ther are many diferent Kinds of symmetry, for example the aymmctry of benaene in patently diferent from that of methane, {yet both are im sme sense symmetric, Only when we have pat the “Sononpt of symmetry on © sound basis, will wo be able to saaify ‘moll into various sjametry types (oe the next chapter). ‘The way in which we ajotematin our notion of eymmutry is by introducing the eoneept of w symmary operation, hich ln ah action sbich mores the miler framework into poston inditingwibate Tom the orginal one At few night fe would appear tha there are ‘ory many each operstions poate. We ill ce, however, that each falls into one of five slaty delineated typer! identity, rotation, Fllection,rotation-reflection, and inversion. lat to tho symmetry operntion wil be the symmetry element "These two term are not the mune and the render 8 warned nat2 symm Options onfose them. The symactry operston lan action, the eymmetry ‘ionent ina geomet! eny (0 pols, aise of» pla) about which S-ttion ate pace. Tei worth tenn hoe that one ofthe probleme {a the theory af sytney I the onfurion over the meaning of word, tome of which have a general meaning in everyday lip But © very [resins one in the theory of this book. Further confusion aiss from {hove ofaymbols which have one moaning in arithmetic ad another ingroup theory, ‘Dh reader ta vined to think carefully what the ‘onde and ayaols in tia text really moan aud not to Jump 2 ‘onstaons Wich thi in sind, wo dsc Initially in thi chapter the Sgsbea of operator. An oparsior i the symbol for a operation (the Swords operator and operation are often wed interchangeably, aad Toogh, sentially, fey should ot be, no gest arm comes om boing). On the arface this algebra apart tobe the same ws the Sigeben of munibers ut a fae Se not. "Kt the end ofthis chapter we il abow that knowledge of symmetry can lend we dtedy to predict whether & molaoals oan have = ipa ‘Roment gad whether ican exhibit optical activity. ‘An operator Sa the symbol for an operation which produces one function from apotor. ast av function fusigea to each # in vome {age a amber fe), to an operator O auaigos to each fonction fin ‘retain cao, ew function denoted by Of (Po dsingush operators fiom other algebraic rymbola we will cburctrian thm by beld face Iai liters) An operator, thro, aa ralo ora means of geting one fenction from another and at the out tia mportant to realize Ui ‘very gest geoerlty; they ean, for example, bo ae spe ae mulipli- {lon by 2 wherein tathewetinl orn we would wie 0 = 2 times sand i © operaten on the function f(2) — 34 then the now function mm (Ope) = 2 ene fle) ~ 29% Other examples te: the diferent operator O ~ dh inal fonction inf) = 2+ then O produces the new fenetion one) = # ‘he aquaring operator O = (Ifthe origina faneton in ft) = 242 ‘hen © praivonsthe new fnetin Ofte) = (2s) mat teats (eta) = tet = Symmetry Operations sn operator O which change the ign of x and yi the original fanetion tere) ~ expleshinly) then O produce the ew fonction Of, 9) = exo asin by); land the logit opertor = tn the orginal fusion {fl2)~ expla then then feetion wl be fe) = tnexpas)} = 0 Clery, there see counties examples of operstors ‘One special kind of operator ft the inser operator. An operator O willbe linear Oy. 4) = Of Oh ez whore fan ar fnetons of one or mare varabls, and sf uy) ~ 207 esa) srhooever fi constant. From the examples given before, ti lar (hat dle linear operator ninco ah ah ate 2-104 ost guns 0%. Of oun = an- ert 0 ae Out bal) # beh Ha Ou = gt) 7 gy = 10. Anthro oper ti salary ope, wl sn atone pea ee aaa itpedet inn unten nosis amaseuoe (iy Aeoedaa the somo tna oes Ocoeh Or ete ot aeremneer ea “ diartor = artrvaet (Te pod ae Toe rn of wo nope ad Ot defined by the equation 9.9.5 _9,0,f, (224) hata yt opntao tn nen fo dan ec Soiucbtapcia et re tented ees ae wait Rater dats search ans meee ina imperforate ae et 01+ 0%10 Symmetry Options umber), and that 0,0, not necarly the same operator as 0,0, (og if Oy ~ djde and O, ~ = tee, then oo Lien ~agenil wa its snd symbolically we write snd we ty that O, and Oy do not commute Incidentally, the reader ‘net conttantly beware site fact that when one write m prodoet {two operator, 0,041 dora not tant Oy liped by O, although (3) The sinccltio law This ean be expensed hy the equation 0,(0,0,) ~ (0,00, e238) hich means that combining Oy and O, (ae ge (2-24) et and thes this product with 0, isthe same ae combining O, st Oy fiat nd thon this product with Oy ex if Oy = 2" tines, Oy — aide and 0, — ata then a 040,099 = ayy ~ 8, sind ag (2.2.6) in at {4) he diatibutive law, Thiel i gv by the equations: 01(0,++0,) = 0,0,+0,0, a ean “ (0,00, = 0,0,+0,05 23. Symmetry peti “A eymmetey operon is an operation which when applied to 8 oleae by which we mean the alee framework) moves iin such a ays ep painting om aa ‘oct on any ply! property ofthe molecule, Ako, in thi text, we STHL stalin the contention hat the operation st applied to the Tholeuls ital and aot fo nome act af spatial axe The rymbol or Sch an operation i eal symmctty operator for shah Bold-aco iit type wil bo wand) For evory syutmetry operation thre i 8 Sym Opens tt coreponding symmetry clement (a punt, a tne, oF © pane) with ‘epee! to which the operation is cursed st. There ar Be dieroat Kinds of symmetry operation Phe identical operation ‘Thi isthe operation of doing nothing (eving the moleale wn hanged} and, at few ight, may sem somewhat grattoun; Ita Inclnion,howaver, in necemary forthe group theory that somes later Te coreespondingsymuetryelsmont i elled th tentty and It has the eymbol (rom the Gertan word Binhei weaning amt) ‘he rtation eperetion ‘This the operation of rotating &molecle lockwise about nasi. 1a rotation by anf bring tho clear Leameworks nto sladenes ith ite the moleoale lesa to have ao n symmete clement sm ‘fold eas of eymmetry (other terme are mfld proper axis an fld ‘ation axa), Necraerilym i a Integer. The x7mbol fr thi samen tnd forthe operator C, I rotation by 2yjn produces oinldense the cle 20 wil otaion by times Sejm fire fis an itege), sich on exis, which will eine with Orie given the ayia Cx ‘The corresponding operator C: canbe internet in one af two wayo: iy tanjnor the applentionofC. times, Teiwapparens that ~ Buinco a rotation by niajn = 29 w equivalent doing nothing. ‘snd hence must be an inter Te mt lo be rae tat for lees ‘outaning the symmetry element Can nt lactuee rotation, by ‘2r/n mnt alo be w aymometey operation and this denoted by C2", {rom which we ec that Ct = Cz", Th axl having tho largest n ‘alu called the principal aia Tn Fig. 221 vo illustrate thee definitions for a equar-based ‘pyramid by labeling the four corners ‘f the base This Ibeling te ‘merely to enable us to ace tnt an operation aw taken place and i ‘ano physical signoane: th whole pnt of the symmetry peration ‘thatthe inal erentation i indiingushabl from the orga eee OF the operations shown ia Pig. 2-31, only thee, excluding Bare Aine: Cy, Cy, and Cy Te is conventional when choosing the ayrbel For rotational operation todo mo in auch © vay thet naa sala Domibie, © Cy i sed in prferene to C2. Foal, te apparent that ‘uit often symmetry elements wil soci and i euch ease we will, link ho eymmetry sloments «the Ou Oy end laces in Figs 23.1 will be weet a 0, 02PP PP SP Symmetry pwns 13 ‘he rftction operation ‘Thin in the operation of rection about plane. Ifthe railstion brings the nuclear framework into coincidence with ful, the moleoal {= sad to have a plane of symmetry an u aymmetry shment. The ‘jmbol given this ment io (ter the German word Spica, meaning Imiror- Tf such w plane iv perpendiular to the principal axa it Inballnd a, (h--horieatal) and if i contains the principal xia oy (= vec the pane conaina the principal aie ad bits itile Betwoen two two-fold sxer of eymmctry which are perpendicular {the principal sa ti abled oy (@ = diagonal or boda), this Tatler plane in jot 6 apecal kind of, We notion that rofcting « tmolecal tie inthe sure plane brings Tt back tots criginal potion fd we can write ot ~ Ein Fig, 2.3.2 we latete thee plane fora otahodron and w aymmeti tripod, ‘Phe rlation-refection operation ‘This inthe operation of clockwise rotation by 2e/m about an axie followed hy tofection ins Plane perpendicular Wo that axis (ot vice vers, Uh order ie act important). If this brags the molecule into ‘oineidance with al, Uh maeou ins to have aw fa alternating ‘Sts of symmetry (or improper axis, oF rotation rection axis) 8 ‘Symmetry element Tein th knight's move’ of symmetry. Tt symbol {ind by 8, and uated fora tetrahedral moleale a Pig 233.4 "ein clear tht ia molocala bas» C oxi and plane of aymumetry perpendicular to that xia the O, axis ib leo 0, axis, Te aly Sen thatthe application of S. twice i the wate athe application of {Cy twin (the relloetion part of Sa wimpy ancaled); thine written ot sae In genera, applintions of S, wil gre Shoah eiodd i Sh-cl) ekivoven \Consequentiy $2 can only be interpreted asa rotation C2 followed by © ‘dertion inthe herzontal plane I i od; the opposite la toe fog. rotation by 2,2 pu election in written ae Stand not xa St (hich would simply be C3). Furthermore, simple argumeate ld 10 peraror oo Areatoy edad temewers o> 18 ie apparent that Sy and face te apo of enon wie he equations Sham itm inoda ten produce oer yperaions eg, P a ie nai {ind @ ave symbole for any tro spent opaations then PO i theoperation of Siw applying @ and then applying. Notice the co: ‘tion that the Bit operation to be eared out in the one on the {Heit Since both operations, P and Q, leave tho moleeul eoicident wrth ite eo must tele product and therfore the eomaination of two (or by extension, more) symmetry operations i Raa’ = symmetry ‘peraton, Mathematically, we may write ro-R ean sd say that R i also a aymmtry operation. The order of the tris coer gf sportant since symmetry operations do not alwaye fsymmetro tripod (ee Pig. 2-41) GG = and GCE ean ‘Tasne 2-9.1 Symmatry operations and clement rena ot pm pine of ney pA pln sent prei ecicar S paca ape “pnp a mmacy ot18mm Operon snd banoe Gy and 5" commute (GG;" ~ Gi'G,) bat spd hence C, ano, do not commute (Cye, # 9:6). The panos 2, and of are defined in High. 2-3-2 and 3-41 ‘Symmetry operations clearly obey th anocative law (POR = FOR) = POR, 43) {cto apminetry operations combine together to give the Metical operation Beg. eg (242), then they are anid to bo tho inverse of ‘ich other andthe invore of an operation Pi writen at P(e have, infact, already been unknowingly wing tht notation for rotational ‘poration, ef: Cy and Gy", the genera itaaton a written a 70 -0P - 4 in the inverse symmetry operation to @ (P ~~) and PA eymmetry "Tne invere af the prodt of ro epmametry opertions PQ ia Pani (wort — or. eu ‘Thies cen too teve by noting that (OKO) = POOP = PUP = PP In carrying out the above steps we hare made asm ofthe fact thet, the “do nothing” operation, can always be dropped from any combi: “Although there eno prota for dividing ooe operation by another, swovcan ehvaye combine soo rronoetzy pesca with tho lovers of nother symmetry operation sad ths ie ewendaly equivalent to ‘ivan, eg, thoogh wo eannot change PQ ~ to PO/R ‘combine both sides withthe rymmetry operation R-? and abla POR" = RR*=E. ‘Th radar should convinse himself that the iver of E, Cx 0, Se, san fare respectively, B,C, 6, Sy and ‘Fialy, sword of warning; beeatoe the onder of opaatios in « product fo important (Wi one tthe ight always being carried out Ton coe anne be corfel when mnpulaiing sguntins invelving symmetry operations, for example, if PQ = R then wo ean Write TPO = TR (combining Ton the lee of bath wide) or POT ~ RT Srameey Operon 18 (combining 7 onthe sight ofboth side) but we cannot write POT = TR of TPO = RT. 25, Dipole moment ‘Ono application of symmetry operstions that we can make right ssray concara dipole momente‘The ua oftymtstey argutente ea, tellus whether a molecule has dipate moment and ia many cnee ‘long which lin tin Since symmetry operation Iuven» tleele ically ind ‘nua a w-fold ani of rotation C, te dipole moment must along tis ‘tie but if we have two or more non esincideat symmetry ate, the ‘Molecule cannot have dipole moment besasne i catinot lie on two ‘see at the same time. ethane CH, bas four non-cotneldent Gy ae od thrafre has no dipole moment (ow Wig. 2.61) 1 ther ia «pas ‘taymietry othe dipole tomar saat an ile plane cad there ‘ro aeveral tymmetry panos, tho dipole moment mist le along the {ntermction, In ammonia Nil, the dipole moment lee long the Cy2 Symaaey Operation ‘tle which ia alo the intoreotion of thre eymmetry planes (eo Fig SCA meen containing a centre of eymmetry & cannot ave & Aiple momen, since inversion rorerna the dirwtion of any restr. “Our conclusions sbowt dipole momenta ar ll within the context of the Bor Oppenteimer spproximation and methane, for exampl, has Invoulty« seal pertnnect moment whow magnitede isthe oder of Yo"rtoio'*D, This moment i caused by contigs distortion efectat 28, opt acy ‘The origins af tho subject of option ativity go back to T6n0 when ‘aygonn dacovered hat ight cold bo polarized by a doubly-refracting {ystal of Teun spar (clita), Detaled dveriptions of light pola {ition are evaale in many books and for our purpoen itis only ‘Dooumary to real that in cour polaaation, the elceic vector ‘Coociate with the ight dosrboe a right or left-handed helix aod {ln ifs right and» lf coolant polarized ry of tho nme frequency fre supenimpons, the roatant slectee Bel voctor is a une ware {fenclin along a single dveaton (plane) im epace, Sch ight ned to Derpane polarized. ‘any tubers can rotate the plane of polarization of «ray of| ‘plane poland ight: ewe oubstanoo are aud to bo optoaly activ, ‘The tt dtaled scaly of thn phenomenon wos mado by Biot, who found tot only the rotation of the lane of olaiation by various haters (ototory plariation) bt lao the variation of the rotation ‘Tih wavelangth (otatory dispersion), in work wae followed wp by Pasteur, Bite student, who separated an optically inactive yea ‘ater (eodiumn simoniem tartrate) into two specoe which ware of ‘Eitrent crytalline form and were separately optically active, These ‘Gro open rotated the plaoe of palaszed ight equally but in oppeite ‘Urwcione and Pasteur recognised thot the only diferenc betweon, {hom wan Unt the eyeal form of one waa the mirror Image ofthe ‘tier. We know today, in molewar term, tht the one Receanry {Gnd euticlont condition for a bwtance to exhibit optical activity be that ite molecular structure bench that canna be euperinpowed oo fas image obtained by reflection in » miror. When this condition fetid the mcleule exist in Or forms, showing equal but oppodte ‘Cplsealpropertios and Ue tro forme ae caled enantiomers ‘Wether melcoue i o a not superiasposble on ita riror image st quetion of aymmotry. A molecule which contain « wold alter. ating axis of symmetry (S,) i alwago auperimporble on ite miror 1 ke, Pl, Ea 2,50 (1, Simmer Options 21 image Thin a tron baton the operation $, coin of to parte: & yotation Cand rebeaio w. Sinn »roection rates the ior Itmege the operation 8x aguas to rotting in pace the mor Innge, By deinen,» molrlo containing h Sse 'ntroghe ato twincians with ei bythe oprsion 5 sd heave te mine meg, Aer rotation, in sepevinpomble Tho mdr i nade that Sys tnd 8; = 4,0 that molecle wit ether «plane ore centro of aya tmety i alae optioaly tative However, the meat general lo» Ileal with =, neni opty louse. Convey, i can be ‘own tat malelewithowt yan ning aptly save ‘Phane ad ants of smite} are eaaly inti od motets aving thee eyminetry laments are Tay sawed at native; sitorating sxe of symmetry (with n> 2) can be harder to apo. ‘The fiat exh of moles with «5, axin (> 3) t be expr enya a3. nt se rin i 188 oe Fig 2-81) Thin lon han Sata ad aut expec, found to be net aa Fie 63, 4 aap. ip et.Seoukd a i [coon Mrmr rs opi on mt In principle, the lack of « S, axle dictates the existence of optical ‘ctvty and two example aro giv in Fig. 2-82, bowover, in pacten, ‘muy not alwaye be pombe to actually demonstrate the ectiiy. "There erw tro reams forth, One i thatthe opal sctvity may Bo so stall hat ie vrtuolly undetectable; tia Uo cae Yor the 0 eb | Ep TE Pce ob cal seg at forma of butylathylhexylropylmethane or forthe twa forme of the ‘baited bipheny in Pig 8 The lack of activity in then moleslen ‘an bo acribed to tho fact that there are only etal dfereneea between {he sobetituent groupe. The srcond roan in that fico rotation co prevent distinction bolng ade. For example, the mbaitted phenyl molecale in Fig. 26.4 has rotation about the sntral Bond restricted by the nro-groupa but nevertoleas rotation of both end {r0ape a8 shown in conformation (a) given ie to conformation () ‘hich i complaelyeaperimpowbl on {c) the miro image of ) In ther words, though (a) and (a) are not soperimpouble, (a) can BO onvertod to (b) = () simply by fee rotation “The ender evi that opti! activity alluded to again at the nu of the next chapter in problam 37 24 ah moans 0, NM nd Cl Fo ee eae Spake more City Ce cD es, ae ONS UOy ofall et Galen; mone Corea “3. Point groups Tn thie chapter we wart on the long path that takes us from the ryametty coments which» sleese powouea to the theorems which ‘WaT reduce the labour in qoantamn teshanical eneultions, Thaw Theor form a part of the eabjectealod group theory and the ‘Connecting lnk Intween group tory and the metry operation of Uholeale i thet the itr form what ix Knowa ae = growp. Thi ink ‘Spear up the whole westh of aleabe information which a contained group theory. AU vt aight, group theory appear 20 abstract and ‘2 Snvlated to physical reality that i meme amazing tht abosld ‘be tho powerful protic! tol which ii ‘faving defincl group and given sine extmple, we wil conde the ape typo of rvap which ln of interes to wet the point group ‘We wil then intron the notation wich mart bo matared and which {ow us to asl molecules scoring tothe eyrametry elements they power tnd re wil gives tiple ashome fr determining the point Froup to which w given molacala belongs: Once this cafeation of ‘oleeslen has been thade, wo wl longer need to consider apeiic Taoleeulee but only bedi having eotain symmetry proprtic, 16. Delonging to» particular pot group. 22, Dion ot group ‘A group is any wt or coletion of elomente which together with some well-JoGind combining operation cbay » certain svt of Tues. The Toening of the word ‘lees’ Yer gooeral. The someats oocld, {er example, be numbare, arise, voctor, roo of an equation oF tmmetry operations Tea important to remem tat the dedniton Gre group requres epecliyig ¢ combining operation Tha to i quite {mera It ould be, depending on the paricalat group, ordinary Ratton, ordinary mltpliaion, matrix mltipiation, vostor ad ‘ion, or one operation followed by another. "The rues wich tho sleects of group mnt obey aro aa follows. ‘The ‘producto omabinaton of any two ements af tho group most produce na caman which alos member of th gros, Leif P and @ ERiymmn fortwo member ofthe group and P@ = i, then moat oe momber of the group. tice ar PQ doe nat mean P multiplied let rps 28 boy @ but rather P combined with @ according t the defined combining ra ‘The group must contain the identity lement, which ie givan the symbol B, and is each that when combined with any element ithe {roup F i loves that element unchanged Le RE = RR. Note {hat commaten wih all lmenta ofthe group "The amoiative aw must old for all lements of the grosp, b2 POR) ~ (PO)R. or, in word, the combining of with te sonblon tion QR smut be tha ate atthe combining of the combination PQ with "Bvoryelamont must have an inverse clement J which mst also be mombor ofthe group, The invere def by the equation: BR "hav for ole ace put into compact form in Table 3-21 Tasex 2.21 Definition of 0 group 2.3. Some sama of arms ‘Tho preoding definition of « group sera rather abstract and “xontinglyganeral and in order to Bing things down 0 earth, we give {mths action some conerela example, All postive and nepatve whole number together with nro form 8 ‘700p how combining Tle ie algebras addition. The fist ru of © {reap i obeyed bneniae the addition of any two whole numbers ‘Produce another whole namtber whith i, by defi, nana shment [tthe group. If we add sero to any whole number, the somber ie ‘unchanged and sor this groep th Hantty clement in xr, and this to ina member of the group. The saiotve rua cles bolinand the Inver of any number irly the agave of tt nunibr sted thas tlio an elemeat ofthe group Le. a-+(~a) = (=a) a'~ 0. Ther are ‘Se in ite numberof elemauta in this group sd for tia roacn te ‘led an nia group. “Another inna group cosine ofthe vectors — al-+H-tek, where 1, J, and k are non aoplanar vector ado, fy aid ¢ see ponive ‘ngtive whole numbers or soc, The soubining operetion la Veter24 Pein Gramps sition and the Mlntty element ie the null esto @ — 0 ‘Another group const of the slomeots 1, —1, Land =i (where 1 YN) tad the combining operation of algebraie multiplication Combination, or mlipleation, of any two semesta proces one ‘he four elements athe demity cement; the acl rule hod; fod the Inve of Lely of “1 it ivf tia wip of tink Thin ‘ample of «faite group "The rota of the oqution = — Late 1, (LY/3—)/2 and — G2 41/2 sod ifthe combining rales algabes rotkpiction, thes thee ‘embers forse «group for which B ~ 1. 'The dover of | lat and the ‘thee to lane are Inecan of ach ober ll powers of two, 2 27.2%, 28.2%. form an infinite group if ‘he combining rala to agobeale tultpinton. "The four metres Jo 1 0 of | 0 0 of foo 1 of fo o oa ooo tf foo of [1 oo of fo 1 0 0 {orm finite group if Use combining rlo Se matrix maltiiaton. Tn thie exarple theft matrix the deatity element B.'Tho mali ‘ation af ay two matrace prods one of the fut. The algebra of ‘matron is daoumed inthe next chapter 34 Plat pou “From our pint of view, the mort important type of group i the one which consine ofall tho symmstey operations (nat the symmetry Clements) pertaining to molecular struecuro, For auch a group the ‘imbining rule one persion followed by soother Since the app- ‘ton of'any symintry operation loavee s molecule pysealy un ‘Ghanged and with the ase ertentation in spac, It contre of tans ‘tals remain fed in apace nde ll eymmeaty operation. Prom {int olloes tha all the sen aod planes of apmimetry of « molecale ‘turt internet at st lenat one somoron pont, Such groupe are cllod point groupe (Pot a ryeal of inte sae we sam have symeley Cperatonn og ttaations, hat leave mo point Saad in spec; thaw {ire rie to pace grove) "That the aymmety operations of « molecule obey the four rle for & cop in ely veriad. Tho somblnaton of aay two aymisetry ope ‘Sons mort prouce another aymetzy operation (oo (2-41), the iat rome 27 ‘entity eloment is the “do nothing” operation the amosiatve law Folds (ao eae (2-43) and eomesponding to each symmetry operation ‘her san inverse operation whieh anna ta ofc and which leo ‘symmetry operation and therefore « member of th grovp. ‘To ilustate thee concopts lot us consider the symmetric tripod framework (hia ha the sume aymimatry ae NH), In Pig. 941 me show the following six aymmetry operon (0) do nothing 2), (2) rotecton in tho «plane (ef), (2) rection in the of plane (ot), (@) reflection in the of Blane (2), (6) dlockwise rotation by 2/3 about the Cy aia (Cy), (G) clockwise rotation by 40/3 about the G, axis o anticlockwise ation by 20/3 (Chem Gr), ‘Notion that th nymmery elements with reepct to which the operations sc caved ou, rom fixed in wpac; Ut l,i we introduce « xed bet of laboratory ares (e-9, 3) then tho operations an be defined ‘Tih rpc to thee atte @ de the ye plane, ofthe plane oon {ining the = arin and 20° cockwbe from thee plage ete, I in alo {important to undarrtand thatthe labels (,,e) on the ft of the ‘ipod havo uo physiol igieanee; they are only convenient way of ‘atitying which symmtry operstion hus been carried out. Tn the light of what comes intr, we wil awayy coir rotations in ‘hele elocwise sose ego wl interpret Cyan a lckwin rotation ‘of te/3. Purdue, in all operations it will bo the fody which in ‘moved not the nt oflabortory aut The reader eatoned that sre {ext books take the oppose convention and kop th body fed while ‘moving the laboratory axe tall mas down tothe same thing inthe long ren but Intertndite stpe wil Took iferet, epocaly with regard to the sigs inthe comeeponding equations For this reason, ‘en consulting anchor bok, always cbeck the convention bung wed "Tho ax operation forthe symmetric teipod form » patieuar point ‘zoup and the way in which they combine together a conveniently ‘Tummaraed by what i known ar group table (Table 3-41) In thin ‘bie the operation to be fw cared out in given ihe eat rv sod ‘the second operation tobe exit inte frat colar, the ore ‘on falla in the body ofthe table at the intersection of te ppropriat row and oalumn, 8g. 0,6; = Cy hatte the operation of flied by the operation ef is Honicl tothe single operation Cy (oe Ig, 34.3)“An important conoept concerning groupes eomorphiom, Two groups, 1 with the slomente 4, Band 9" with the hrnente dB ‘td to exhibisomorphiom if» one ta one crreepondence Ava, Deed, ‘can be ertabliahod Dutwoen thir lament much thet iplien 4°8" = sn vie va, oF more bry if (aby = Paraphrsing thie dation, we may say that saomerphic groupe here (goop tabla of the mame atractare or form akbough they muy der In aapect of the notation snd nature of thir eementa and dir ix‘aie combining rales. The flowing two groupe of order & are Soo ‘morphic, the combining rule for enh beng lato in brockets 1, =k, AL. (ordinary mubptcation) (matix maliptoation) Iden ithe slmenta ofeach stare renamed 5 Ay B,C (i thinorder), their common group table in non to be Bape s{pape ala non alpora clo ras Likewise, ifthe lementa B, A, B, ©, D, F of some group combine ‘ccording to Table 3-42, whi has the ane structure aa Table 3-41, A group table withthe wre structure ae Table 3.4.1 "in iomorphim each element of One group i wigualy mirored by a cleat of the other group, he. no\two elements have the mane Image, The more general stuntion, alld Romomorphion, ill preserves the stractare condition (43) = 4°5" but ineudos case in which fo {iran slemeata of oe group @ have the ame image inthe other {700p 9” Than in lomomorphir stractare ia rained but individually Say be daatroyed. To mention » tval oe, any group 9 ls bomo. ‘morphic with the gop 9 whou only elasient tha amber a fat Boi Banh, Goh 9 reaton ofthe form a ~ 0 la eatied (er Sato 1c = 1, whieh a eidealy tev Tn § 6-10 wo will ae that for group of equare matczes thee is always « homomorphle core ‘spondence between each iatrs nadie determinant, 24, Some prope tens ‘The member of elements in group la called the err ofthe group 08 In unally given the symbol g for tho polnt group for the ‘ymmeeio tripe gi 6 and fer an inne group Tt in lar that the slots of point gre to not necesarly ‘commute, that is the ordar ln which ore corte two aptamer? {erator ean be important (ay for sacepy Pgs 24% an Table BA wine for th amie gd Cho yA grap fr which ments do commute sola a Mel ‘One san, of soune, combine wore thas tro cant soup; one simply uae the given combining rlo more than ence ©. POR ‘bined ty combining @ with to obtain mm ctor cement of te troup and then combining P with ths slement 1EP ea Qe cant of «ru thes wb te don of 4 romp, i the inverse of @, @, ad eonaoquectly QP. I his ator ‘bination ie dente! with he somone ne fan we R= ore won fd we say that 2 inthe traiform of P hy Q or that P and R are ‘onjagte to each other. The eitaron,therer, for tw elomente P ‘ato be conjugate to oach other ia thet nga (0-81) hole for at Teast coe slament Qf the group. Wo ean sonsbine Q and @-* on the Jef and righthand sides respectively of both aiden of eg (281) and Produce GRC = Q0-1PO0-* = EPE = P. @s2) Either of oqo (61) and (52) sta a Sno of xaugntin bars oe damn fs prop Farrag og ‘oi gis conjugate the Pm onjogui to 8 Tn indomsare by the following equations: a Pexor, on rar, endorser mre FOR, (mom 249) snd an YX mut be some slmtnt ofthe group ay Z wo have PRs, (5a)2 Pala coe ‘The cements of group which are conjugate to eachother are mid to form alow and the ormber of rants i the th slam in given the symbol g. For the rymietre tripod point group the element al into Gn Ge" with 4 = 3s o4 = 9 aod go = 2. ‘or thia and all groupe B ib conjognt with fmf: X-°BX ~ B (al X) ‘snd noe Zio always in clan of te own: we wil alwayn sonar E {eke the int clam Phe render, withthe ald of Table $4.1 am ent for himeelf hat iQ = oor oor a; then with any ofthe sx elements ofthe group X the transform X~1OX ls ether oy ot wo of aod that .Q'-"C, on G5" then with any cloment ofthe group X the teslore 10K i lth Gy oF Gy ‘Any element wil alwaya be sonjogate with lf ae Bis always in (ts group and P= BODE, "HEP and Q are conjugate, then ao are thet inver; tia follows sng eqn (24.0) fore Ps cgay = (exp Tioxyx gx. ese) ‘Hienee the inveras ofthe oloments of clam Delong 10 sas (i ‘sometimes the ame 000) and the order of clan of elements aod the ‘rer ofthe cam of thir iver i the ane. a an Abatan group, px = xoxp-P, ‘and each sloment sina can oft own andthe numb of eam the ‘ne a the onder ofthe group. ‘The technique that har bao given for diving any group iat clatee ‘an be rplaod by» sinplr one inthe cue of pole groupe, Tis is ‘aloable ince the teting of ye (3:81) forall penile ombinatons 9f Q and P of a giv point group can be quite time conmuming, ef ‘te equilateral rangle belong to pint group which han 12 nytt ‘operations and therfore for this pint group we would have co work font QPO 14 tines, That there should be a snr way iw indinted Dy the face that inthe example of the symmetric tripod Pst grou Biren above, the dass appear 19 be a “natural” wehdivnion of the ‘Point group and to contain operations which ae ‘ar “The following wimp ral ean be ertablaod for polnt groups (0) The symmetry operations Bf, and Memive (2) Tho rotation operation Candi inverse Cz" wil Halong to the sine sane (a diferent laa foreach value of) provided thee ie ‘re each in a lane by Pant rome 3 sither« plane of symmetry containing the OF axe or & Cy ain St right anges to tho Ck axis if ot, C# and Ce aren lata by Shemmetves fio fotatioal operations Ch and CF or St aod St) ehoat Aliforet rotational are, 2 the two operations belong tthe ‘ame elas provided thar sa symmetry operation fn the plat {Boup which moves all the pointe on the OF (or St) azn to fSoresponding postions on the Cz (or 8) wx The prof ofthese three rule Se Dane on Ube relationship with ‘og (2.81), The symmetry operations E and, commute with all, the other symmetry operntions ofthe puat group of which thy area part and hens, iP — B,4or 9 and Q in any aymetey peretion of fhe given point group, Q-iPO = Q-4QP = P and P in in dan by ita ate (). "The prof of als 2) and (9) depends on the fact that the aymmetry ‘operation Q-*PQ must be of the same general type, rotation of ‘ston, a P (this in eally demonstrated). Now consider the rtatonn (Gh and Gz" fora pnt group which cootane «reaction operation @ ‘where the plane of eymaetry ¢ containa the Of xia. Th eymetey persion a'Gfe, or aCte since e-! oy muni bes rotation about the Of axis wince pois on thle gala are unmoved under the three ‘omponent operation (2, Cte) and the only quation remaining t ‘the magitudo of thi ottion Ta Pig 3.8.1 in shown what happen te the rectangle OABC under the symmetry operation e'Cre if (Chis a closkwin rotation by 6 dogrens nnd ot thas Pane; i eae ‘Sat OABO ts rotated antlockwino by @ dagreas, Hence the rotation fC must be Cz" and Ci end Gy" must belong to theme sam In Fig. 3-62 the operation "CIC G.CZC,) eared ut This copertion must alo be «rotation about Oh aioe ponte on thin ax hd up by being samored. What happens fo the rectangle OAE Aemonsteaes that Cy'CC, ~ Cy. Thew remit, togeter with thar ‘extension to rotation rootion operation orm the basa of Rae (3), "To prove Hula (3) nee sonar the radeon opertion Q-eQ ‘where Q iso symmetry operation whish moves all the pote os soe symmetry pane eto corresponding positions on the eYmmetry plane ‘© Taking the components of Q-"=0 one by one: Q wil mare theP1036 Th it tc ang Pon A, Ph oy nl mien ois tC ai eee Piet Grou 36 point initially in the plane to the « plane, « wl lave thoes pointe Snehanged acd OQ will move tha points back tothe ” plane, eno, {G-100 tnaves te pointe in th o plane soved std tnt therfore tb aatetion in that plano, ie Qua == and o and oblong to the same eae. Now consider th amie rue fr rotate if Q ores the point on te O&axin vo corrnpoaing positions om the Ch in {en CE wll are them vnchanged and Owl bing thm back to ‘hale fil pontone oe bout the CY axis; the magnitude of thn rotation ean be sean by Sgprdering what happens to pos in sty plane which sortainy the (CE nxn Tf ies rotation, then Q-!C20 vill be 8 clocking rotation Dy Haxjm about the CY akin that a Q-'CZO ~ GY and Gf and Cr Delong tothe ame clas 1 Qin rlecton, then O-1C20 wil be an sot-locorins tation by Ey (eee Fig. 3-53), but sino for til hold trv. A smi proof exit for rotation rection operations 216, Clasitenton ot psn rope ‘We aro now ins postion to describe and clamify the various point sroope hat exit. The notation we wll un shown so the Schoenfce[sssssasegee 2 since e Rcpersech ct ouacBe seat Bae oy Gepemnin te ye oe resetES eS ES Saemie nat ase eo ee ‘the eymmetry clomeate for osch point group ia given in Table 2-6. ‘nd in Fig. $64 we show some molecular example, £17, Deination of molec pint roape ‘With experience one come to reognize the point group to which » smolecia belong timpy by soalgy with some other Known, molecu However, until one builds up s memory fle ofthe pot groupe of apronmtative moloale, ti ost toms some method. A ‘heme which will enable the reader todo thie x thown in Tale 3-7. ‘ted todluntzet how i work, wo wil soni tree typical sue, "Tako, for example, the boot triatomio moleele AB (en, 1,0). Following Table 7.1, in not linear, doe not have two ‘more C with 9, dows hnve'n Oy aa bt trea not 0, ses perpendioulas to thin axa, t doa pone two oy (vertical) Bahon ‘hertore mst belong to the fy pist romp. ‘Next, take the tqoare plana telece Aly(ey, PAO), iin nob liner, i dove not have tro or more Oz with #23 (though it doee ‘havo one), ite principal axe ia , and tere are fur Oy axe perpen dicular to this axis the plane of the mola no, plane and therefore Wu belongs tthe qe point group. Notin that tia tolesle alo ottomos vg planet, Bat the oy plane i enough to smote i with the Bq pot group a Finaly, consider the puckered octagon (44, 8), i i not nea, doce not have two or tore Oy with m 2, ix Pineal aria ged ‘era four Cy ase perpaniala to this aa, thr i no y plane, thes ac, howere, out o Plane, the molec commenti blogs‘Eo‘Gitam having a Whe right mmr ef toe sooaton, We weal pies and D are tno dirt elamts of he group, Combing ots Thee oqenins with Boa tha ight hand ss ach ie ean oes ore Abe = FBS DB = FE Sept enti 7 xa a sine Hi 2.66 ant H-01 pa eee ae ith aga lpnane 9-701 Af chart for determining the point group of molecule emo Heac Fo ay ct amen cant ape tvic in he ame snd becran sac tow sou oninng he sae number of Sines abe be grap a le ‘cm Oh on Say of fe fring crater empoun SET Saka aCe (one Sty sea, Grae ‘eoring te Hy Gy one fara ot cpelsasace Ss ee om “ ee pe of te owing aa ea4 Maices | Ws have shown how the aymmetzy operations for x molacae form point group and we have lntrofuoed the atin which allows to ‘Samy point groupe. The next stop which loa to farther progres to find sta of matrca which behave in fashion tsar to the eyo ‘etry operatonn; that In matrves which are homemorphie withthe symmetry operations (ce $31), Theno matrices wl be mid to represent the eymmetry operations. Matte reprenentations of moleular point ‘roope paraphrae ins thewatial way the aymsntey of a moleenls {Sod are central to all our apllatoon of group theory to chosiaty. ‘There are many theorems im mathemation onoering mate rope ‘sentation ad once tho link between repraentations and point ros Thee boon made, the thoorere ca imeditely be tke fr eolving ‘chemical probleme’ an diferent ae the meleclar svital theory of ‘benno atid the elastin of the vibrational level of methane ‘But blore we cas dacum thane matrix eprentation ta noteany to understand something abost the propre of tation theralve, ‘Therefor in tha chapter we dene © mats, daub the algebra of imatrcescnd introduce the mates sigenvalee equation end the ‘abject of aimiaity traneformationn, The reader who ein we ofthe large number of deGntoor and theorem ta tia chapor ay, if vwinhes, go traight to Chaplar 6 aad then pick wp the material on ‘atric in slow stages auf foquted Inthe scouring chapter. “Tho various theorems fr matstcn aro proven in the appendies 0 thin chapter but thowe proofs re not eatin forthe understanding of fature chapters and may be ignored by the fener whe finde the rmetherstie too Beary” going. im Appendix Aci crt spacial ‘atrioe and rms ae defined and these wil crop up in the fre; tho reader is therefor adviaa to take Hira fine with them ‘hay are summarized in Teblo 1.1 £2, atten (men ond decries) ‘A matric ies rectangular array of termi (aumbers or symbols ald leneato which are wotten between parnthones or double nae eg Cease Tans 42 Special matrices and terme a ‘There io a daft algehrs soocated with mati (es § 43), In thin ‘book we will only be concord with square matriar (where the umber of owe equal the ruber af columns) or with sigle row or ingle colon mattis, Wo will use the double line notation, eee a, ay Aste rm nme an [24 can be aed to define the components of vector. In general we wil ne capital aie letter to yl 4 matey and-an element in ’th yw oi eu fms Awl en a “The numberof rows (or columns) in 8 aguare montis called tho "The render moat nt confuse aquare matrices with determinant A Asterminact tm square array of laments symbolising the num of ‘ertain products of the clement. Ualie a mati, a determinant ha © [i Sanna wan Seasons te stn ie oo eibee ad abies odes —aiea— ody 1a poneal, = determinant is equal to the mum of the product ofthe lementa in any given column (or row) with thelr coresponding ‘ufectas; the costo of an lament, yy the determinant, of next Tower order, obtained by atrking out the row # and the column jin srhich the clement i, multiplied by (1) 0g mee a Sls q ties —De) eber—be) sci oom Marie 68 nee, we may svcoeanively break down any determinant into products {nvelving lower order determinants, unt seond order determinant are ‘achod, the values of which are given by eqn (€2.1) “The determinant of w aquare mutts i the dtorminant obtained by onsdering tbe arry of eloments in the mate as determinant; if he matrix in wre wil write the determinant ae dt(A) ta Aa dy Ae Ay Ae on Ae as thes i 4 3. ate ie ‘he algebra of matrices giver ral for (1) equality, (2) adition and subtraction, (9) multiplication, ad (4) aividon” aa wall an (6) 40 ‘teociative and « dietetbative low. It slo inched dation of (8) = (tanspowe, adjoint ad inrorn of sate "O) equality. Two tntsioce and Bare oqual if, and only if, Ay = Bi for ald, seen] Tfotanneer-[ th (2) Addition and subtraction. Matric may beaded and abtrastd cooly if they arw of th same dimensions Under thee scemetanoen, the wum of wad 2 i given by the metex C, where Oy = Aap By forall andj EE be5 Maven Under the mae crcametanoay, the eubtruction of B from A produces the mate C, aa rom this, follows thet moltiplying « matric A by a mamber€ prodvome mets Egg. show clmenta ar given By By = ey forall andj, rey ys 6 eee ato fo (2) Malpication. Two matrow A ad 5 may only bo sealtptied together (ciled mete mlliplication) i tho numberof columns in ‘ym, equals the number of rows in B; tho product lo then deve ‘oe mate aa ter seen em hy he a: os wan for all § and j 1 tho matrix A has m row and m column (an m0 ‘natra) and the matrix 2/basn rows aod p columns (an mp matin) ‘the matriz O will have m rows and p columns (an xp mates). The following equations aro cxamplas of matrix muliplcation LIB PLS ok ee ciese HEIEHEP Meio An uy way of rmemboring how to cary out matrix multiptiction a {oraz that in dang 0, one tks asomeding rows inthe fret maiz ‘multiple vetorally by asomeding clunstn the vcond mts, the 40h row and jh eolutan prodecing the) slement inthe produc, 2 lel Hest ‘he maltpication ral more than once, multipting pis of mantles ‘atime en eg (43.1)) Por the product of thee matron, Dano, ‘the ganerl element ofthe product i givon by Dy = $ Auto oan forall nd j, where +i the number of columns ix A which matt be ‘he sume a the numberof rows in H and the numberof enema in B which must be the ame a the number ef rows ia © (oe prablss ‘42), Notive the restectione which apply to the number f rors ad ‘columns in mato which ar tobe multiple together, 1s apparent from tho example in eqn (43.3) nd (423), that, ta several, matrices do not commute, Le AB w BA. Por thin reason cate ‘oat be taken when mate equations ar bing ‘owt remeater tha, ‘ulipled together can be significa. ‘Ons ofthe uae of matrices sto eprom nt of Tne equation a & ‘ompact form, for example withthe above deinion of trix ull ‘tion, te pole to write the eatin Auduaet Ante = 2, Aust Ande} duh = a wan) Anite Anes dn = 5 bal arex cenurtbermor if, coupled with them egos, eri ao th at of covatins Bute Baia Bala = te Bast Bae Bats = Ye Buti Batt Bat = He | x-| aa Bu Bu Bu “ Ba te Ba ot || Bu Bu Bu * faa (ABye ~ x. "Thin rat can be exproeted inthe folowing way: the transformation fra toy’sisdetned by » matrix B and that of ys to by © mater “Athen the tnenormaton of vo wn dete by the matin 4B. (dy ‘Division’. Au with operators, “ivion’ oan only be accomplished through an inven pros, Kvery matrix 4 which has # non-zero ermioast, atid) #0, a anid to be non-aingulr. For auah, and only such, matics, an Sere 4° can be dain by the following equation Ad =k = 8, ere inthe identity or unit matrix (ae Appendix At ‘atric operation whieh segulvalant wo dviion inmates ty aninvere og if an-o (e310) etre ABE cB ean o A Ob. ‘Notioe that when we mply ega (43.10) by B-* to produce eqn (43.11), wr mateioo do not necmoarly commute, we must do no on the sgh haad sido of foth sides ofthe equnton. A method fr finding the invene of» non-angular matrix is given in Appendix «2, Prom {ie method itn apparent why 4°! only defined when dot(4) #0. ‘This alto impos that only square mati can have an inven, snes ‘only aque mation have determinant (6) Associative ad distbtive las, Those law ar rerpectiay: ABO) — (ABC, (ets) i ABO) = AB+AC. (ens) (6) Tracepone, adjoint and inverne of «matrix, The aver has Deen Autined in (4) shove andthe transpose and adjoint ae dafioed in ‘Appendix At and Table 41.1. The render is lft to prove (0 ‘problem 41) that the trnepon, adjoint, and invarso of the product of {ho matece are given by dh na, eat ma ena ma, e218) a, een where 2 a column matrix (with dimensions m 1) and 2 in «number ‘Or weala. The solutions of this equation, and in general thar wll Be m ‘which are datne, aretha value of & ale the eigenefwes) and the ‘Somerponding caurmnmatroo 2 (called tha vgenvcors). The equation ‘an be expromed in words by ying that matrix A multiplied on the ght by the column matrix = produeee the sume column utr ‘ply multipin by « number, “We oan diatngush between the apreralsletions of ogo (441) with seria sad write the diferent eigenvectors which corepond tothe Aileen gente yy nya yy OF TE to wo ea mop (141) 10 Aneta 6a NB om ean1 lo curtomary to require the eigenvectors tobe normalizad (sce Append At I), dat seed Cane Pat ata . Setwet fenton wean) “This rstetion oute out thowe aspecfous eigenvectors which der smaely by a constant factor ‘hn alternative frm for aga (4.2) it (Aa 0 Ste ay where isthe Mantity mateiz and 0 the nll matrix (ee Appx ‘A-LIU)). For this oguation to have not-tvilwstion (at I ex ‘lading oletions ofthe frm =; ~ 0) ein nocemary that the eigen “tune 2 obey the determinaatal equation: oda) =. ro) "Tho prof of thie ia given in Appendix A. Rn (4.5) i often cll the characteristic uation of matrix and fe etmatialy poly ‘nomial equation inf with rote: dy y= Ae Tho ool of eg. ‘ales, whish guarantee nontrivial sgenweolom, ance found cas be ‘sed, ono hy One, in the aoutson of eqn -e8)coupled with eae (C43); each sigenvauo 2, lending to © comeeponding normalized ‘lgenvector 2, (ne Appendix A). "There aro two important theorems fr the olgnvalues nd eigen esto of eqnn (444) If & matt A ie Honmitan (4 = AY boo ‘Bppeodix A:¢1(), it egenvalzon aro rea aud ite eigenvectors ore ‘orthogonal to wach other if they correspond to diferent sgenvalve Uf the eigenvalues ure nondegenerate (iy 4). Thin rele oan be eee eae al or Satan = ni) ean Movies 97 sod, if wo combine eqn (4.6) with egn (44.3), we have Bek tae Weal provide that in Hormiian and th rots af eqn (44.5) are dant jou (24) dae nt of normal orthogonlegsnrector. "The other theorem sats that tho mates X formed by wing the sigenector oft Hermitian, matrix ais estrmna in antary (orth ‘non of tary mtr, we Appendic Ap). The ot of ‘The mates X formed from the sgenvector of « matix A may bo ‘ed to combine the soliton of Ase Heino a single equation wal wan ax — XA 48) tee tite [Notie tho order in XA not AX; the reader ff bo com thin fst for himaelf Ta ogn (4-43), 4s Hermitian thon of erurae X willbe tnkary and if 4s eymmetic then wil be orthogonal (65, simu aaermtins Ta mutex @ xista euch that 9 = B, a then the matrices A and B are sid to be related by a similarity trans Jormetion Sash traaformations wil be very ingore in what flows Inter Lets immediately apparent that con (1) parallels the elation ‘that exlste between to aymantry operations that bong to th ene ‘am (cee § 3:8) 1 @ lnm unitary tats (en Appendix 41g), hem “od ae aid ta bo lated by a wary tranjormation, ‘hare sro numberof wofel theorems sonerning matroce which ace related by a sialarity tranformation, Tf the maine sad are ‘elated by a simdarity tranaformation, thon thelr determinants ‘igenvalu, and tren our ofthe dingooa! elements) wil be Hental dey) = 8, es) Boot A — tect 2, 53) Trace(d) = Trace a4)satis 1A’ = G49, B — @°0, 0° ~ 9-100 et. then any relationship Tetweon a, B, Oto ie alo slid by 4, BO" ae "Tf the reat of similarity tranaformation ito produce a diagonal rates (ew Appendix A.11()), then tho proce i ealed diagonals ‘tion, tho matrens A and B canbe iagonalied by ths same mati, TEX i tho matrix formed from the eigenvectors of «matrix 4, then ‘ho similarity tessformation X-'4 wil produce « agonal matrix hose lementaare th igenvalaerof 4. Furthermore if ir Hermitan, Thon 2 will be unitary and therefore we oan aoe that « Hemitian tnatsix cn alnayn be dagonaliaed by sunitery teasforostion, ade ‘pmmetic mates by an orthogonal eenformstion ‘Tho Gna theorem isthe w nitary tnnafrmation loorer a unitary ‘These theorems are proven in Appendix A.4-4 and, in Appendix ‘A. we show, with aa example, how a matrix oan be dingonalied poeration (AAA. Spel mations (o)Idntiy matin Tie au uae tit how diagonal semeat ae ality td wow otngonl een are lx: aloo ae be an head Seats ref aS andi seine ned to el at tea Book ny onda ad on be inserted enynbere i any at onto (@) Diagnal mtrs, Any agoare mati for whiah all the off ingonal eee a ee ge since be Dy = O56 45, Dy #0 mS, (0) Rel mare Toe conjagnte comple f* of « umber ov fenton fie cbllend by mplasng Loveryorein/ by 1 Theconuptecomplertmatet 1's Suda ae 4 td te santa of eth tsjguta Comper f ‘he smentn af, bas (40)y (aye Fore tel eal the smote SS eaten therotore ra a (2 yma tie, trp a mai Ace ya Fireg th nmpine of vy aay dy = Ay fo lS ad Th etic ty () Hermitian mati. The arn of» mac Ai tana Oy aking he soltpat Cojagete te ene tat ie in yoda ta. Diathemssasefogsoriy cal 4*the Hermitian jughe td swarve Gi aipine or he aneponed aise of the wintry of 4) The soe ee law a ii ‘A Stermiinn mates one which obey the equation a8 ae a, dy — Af forall andj Pr oxamle,| Kermitan, All Hrmitan matvou mut be agua. Yor ral matisce ‘he cctrcn for tlng Horan cr tymmetie the ume PLES ors) mari tc ay iain he ant ae | cae (@) Untary matric. A rates i etry if adjoint (0) sore) 5 ini sank, (asin al Ad 8. ‘Th cla (or soma) of untry mati are rated toast of orthagoeal ‘onal vectra grnral recor space fr exams, Inter thn ANA = B ood i Shae ee aan, st entender tr ete unfhe te be rthognal td normalised ihe eolumon of fore he orthogosl, icalaeleeten sy iomge a tiabinny b=. esate ‘erally ning AA" = 2, wo dan (asi) (astt0) aun sd it in tt the roar to show that Ad! = AA = (0) Onhopmal mate Arnis orthogonal if ie tranepoe (0 () sore ee Lah oe ens ‘Fo ral matin (a (0) shove) he eiteron for beng rthogona rwitary ‘2 ethen ‘ilenhagooel atom are moar ad semen le * | A462. Matador detaining te ere tame ‘Conier the mogetions Bo Aah Auta a, Mo Aust Aa ct Avs ween Pam hat hate Aad ‘hoy may be writen in mati notation at a] Ae A om dae ra] Ysa ten 4s La2 evien or Y ~ AE. Maptying both side f thin wation by A" he iver of Sneak Sa or ee he ig Aig os A a Pie Aeon acd Pa yt een soll acs ate Now the determinant of doa be min a an Am Ase aaa) = Aili Tt ot ha a Aint dail dl Ait Aah Aas where fy ithe cofactor of fy en $42) Hf we mlpy the fet of ea TRERI bya the accom by Ses hash by a ln we atc ate by iit Aaah Aaa Heit ttt ae Hitt Aaah tate meas, An An Aw om a Sine detarminacta wih two oF mor oni cnn or rors ar tt, ‘oregon bene Lt aH ae att, (aaaa) (sen 1 the me fashion, wth te other enactors, wo ohn an int ttt, aaa acetate aero aca ea ancl ‘0 that for any equa matrix (Ay eta, ae sree (Tq it the lament in he throw an th slam ft nvr Fe Sa ih te ne amin See oar ‘by mseing ot th th so ccSa cat (A820, ad ttn inv, cant be defon (a) eran A ining fer det toa tart eae, ny Ata ethno any me of» oun n= waa ‘AAS, Tnarame er sgemctare (e) Phorem. 1(3,ar chen a theroolto the agoaton: dtd 28) = 0 ine te ee (aa, . (aaany ‘give non rial lgevectr (clan mato)bat Sabir gat meee ets ca See SR with og (A423), i eta Ang = 0. 1 the column matic to to senate, hes at nt on fit nen, SCE) = 0, Men, for nw vil sane ey 0) tw Naat SoQeulel ie equitse anion (©) Theorem, IFA ie Hermit sgenatoe ae ean ia igenvectors spt ethogna ouch ber road ay comm ono aeprea Prof, Combe oan (4-42) Aas ht (aas2) aking the jn ofthis guation (oe a (48.15), we have SAY = Ape) (ean Aina sola, 1 = 22) a 2A = Ate] (ine A ie Hermitian, 4! ~ A) 0 mulling by, proces sls, = Abate (assay But om gn A432) side dale, (binge malar, icommuten) (434) pd btu of gs (498.4) fom ag (A423) give (2A, = 2 Bins aj 6 foe cm val (4a or Ate ma fh ow Sider the pr of mains es ann tee ing Wn aif land eg on she Ht ha aby : day = Ale = ark, (lace ior assy Apr ee out het and ee ya and ting ssn {0 Farm, Tonner by wing th gare Hermitian “Pr. ‘The eigenvectors ofa Hermitian matrix, if nrmalcod and noe genta, sey tae rion ses = He sad ccogunty we ona wes on 27 — 8 and tarry X1 = Xan X ular, Gorlary, Th mati X, fore by wing the signers af symmetre mst at ia enum sthoponl, Tha lis fo te fort thet Sfenvodr ofa nymmetre mate abe the rin = [Pu ‘AAA Tormey tnaormatins (0) Phorm 1FQ4Q-~ B, then dtd) ~ det Pros. Sioa da{XY) ~ dt(X)ot(¥) (0 Appondis A468) we har: et) = diya 40) doug anc anano) deg atone) = deugantoua) dace) = aya. (0) Phorm, 1@7AQ = By hen th sigearaoe of Aan Bae ania Pre Hem (wan = (G240—18) Tea-ane SBA) eit 4— 2) ang*OneA— 22) oud —a0y- © and dat(B—A8) ~ 0 must be inte, ace Fettsatis (0) Theorem. IC QAG = By then ‘TranA) = Trae Tree) = ¥ Bu FEZ CAA y (we SEA EOWO = FE Auer < SE 4te ~yh a Trea, (2) Theorem, "= 140, BF — 0-18, 0° = O09 ote, then any rultonahip Beton 4, 8,0, a as matt by 4, he Prof. Conder, ana exam, pace = ean0e = eae '20g-09 Zoe 1 a Bae re matriaw whish on be digo by cn es4e~ 2, o'm~ D, her Dy Dy re ingrnl e,n Same =e AaNe"B) a (Gingna marine comsota) =e ene 40) =eiBae sed there AB = BA ad and comme Theron. athe mati formed rom te cgearetes fA, na xe Tiagon tics coupon ote genio ok ‘Pro. From oq 4.8) we have Pro. 439) thea, ‘eter Ai th dingonal matric smmpoand of the sigma of and mole iyng onthe lol's both nw oth equation by Kw obtain delly ura. (asa HCA tu Hermitian, then wil be unitary (Appendix A.) and the {nantoraion se (Ac-4.1) wl be unitary Ate ayes nd te ‘Stnvformation il ergo, (0) Phere. A eaitary tenaformation ners «unitary mates witary Prin. Soe X —U-‘AU, wher A a ar wtary, we bare XA (A'T ooo (43.19) aver im X= (A0y(0"9" ooo 43.18) Sottey. Bat by daiton, Ut = U4, AP = A, and (UY = (UE =U, Te FPL ind la aniary. itewbo, i'd od U ae orthogoonl (al a wll ae wiry) than a le X. grain mir in ern onaider the ingonaizntin ofthe mati fig ‘This maybe acommplabed witha mate X which compen ofthe igus ‘ctor A The diagonal tris arnted wilco ofthe ieanans of [X°Fuestpetnvolrel ae: the dearaiaton of the eigereie 3y ed onda HE) = , 2 deterlation (sing Use egs hus) oF th penretoy EL EF-E Oe eee sa | ete soa Satewat 6m 2.9)ge Ps A—6 = 0 Te ota ofthis aguaion avy = y= 2 and Piery serey ep mtiony 9) With thao rote no can ow be were of non Arial egeaestrn EE Ati = 0 (edandant) faite — 1 (eonmalaton), Trae, a BYE y= Os and ay = YS | | | [ we AnD coma =3 -* 0 —alfaup Jo} 0-1 off =nf—lo tytn 0 ao Art Boe = 0 (rodandast) ytchtrk — 1 (oormalzation. an YR y= 0, and ay = —I/y2 ft nays 0 aya ays 0 —ays| ©) =e yltetiE) eo Append 442) Tum eolctr of Ly, eaux) = yo ~ys 0 ~ys wef “o 1 0 yt 0 aa PSHE Ty os bl i ot on Sete ye steht tte Sept et re sa See {Execs change Xo tbe engage gore sat Sarcoma iPaeuie ‘AA, Poet het dt (48) = et) et) ONSET btn and nt te oun ad of he ame oer aa fede tte Aaa tal AaB uP, AB ABs fie tat [Aa da AaB Aub) LAB dedi Ate adel [dad total Auk AnPal * APs Ando70 Matis Maio 78 ‘The nt nd at detarmnnnt van aon, i the sonata ator Ande 448, Show thatthe mato ‘2 Nemoved fom the it determinant, trons tw desta td wf = va =a a a aya a five Sal © Pave tal sett And Pel At 3 2 ods. a (49, Sh tat yy the geno of A, than Ah Aye i SITE at eins oa = sayy. 4410 Obtain he sigma somali egrets of "The pat canbe extended to mace of higher ene, tat oe matron Aan Ho) Tb = HA, ) (AB = BA, nun nwa 9 revs o} an|-viz ue olf wa o=|—vae ve ol stor tae @-140 i dagen 4412 Digest flame te Sees eg ue ea fe ae oh Sh ee ea Aes nelstel oTax beet way to underdand how the symmetry operations of & ‘oleae influence its properties isto study the sta of tates which Imi, by thei group table (we §24), those same operations, Such fete of mations, homomorphic withthe juin group ore sid bob, oF to form, w reprevesdation of the pot group. Hasentaly, when We fetroduce a matric representation, we afe replacing the lomaty of symmetry operations with the eleva of ratroe. Matrix represen {ations re the eri ink between the eymmetey of « molecle and the theorems which determine mh practical things aa to whe agit Infrared nd ould be proeat or not. Mastery ofthe idea i thin ‘haptar leona to tho proper understanding of mabeoquont chapters “There are soveral diferent methods of obtaining site of matzioe shih are omomorphic with given pont roup aid ita haptor ‘re diooun these methods in some dela. One ways to conde tho (Sot that «symmetry operation hse on the Carexan coordinates of tome point or, quiralaty, on some postion vootar ia the moles ‘Knothr way lato consider the affect that a syanetry operetion bas ‘on one or mare sla of base vectors (oordinaia aa) witha the mole “A third and more complex way isto St find another tof operators Og, which have certain fundamental properties and are homomorphic swlthe symmetry operations, and thon nde mt af rntico which ‘Ss homomorphie with thee now operator. Tis at step is whieved Dy consideration ofthe elect thatthe Oy have on some “ily of ‘atheratial functions («so-called fonction sce) 0g. act of ve ‘hoi of the Oy are bound up with cach other. Ie i important to ‘alae that cle method involve bro stps as opposed to the Rs Ro ‘Sethode which involve ony one ‘inci iseay in this subject to lou ight of the fret forthe tres’ ‘the sce which we are following in thee ltredactory shapers be sutataiaed Ia Fig. 8-11, The reed wil probably find help to ‘oop this plan ia iad while he panne the material ofthis chaptr. or the mike of competane rarous profs are given inthe ap- ‘peadioes but atin Chapter 4, knowiadge of thom i not erica forthe ‘ender who wate to have only general wnderalanding of tho abject, Merc apenas 72 ==s rs =a Fane aaa Fra = 162, Symmevy pation na poston vet |14 ea Rapmataons ofsome point P may alo be leat by ita cooninaton ‘vith repuct to Use ase. (Note that for ease of notation Into on, va willbe utd in prefers tothe more fama ny and") 1, coining with thew fixe wxo, thers aro threo unit vectors (vectore of anit length) ey, ey, and ey then any postion vector p can be ex Premdee P= neinertete (2) [Corresponding to each point in ypce 22, ad there Is therfore = ‘postin vector given by eqn (6:21) and wo can thik inerohangeably ‘of point and th postion vector which define t location (ove Fig 5.22). The mutually perpendicular unit vottor 6, ey and ey oro falld orthogonal base vectors and 2. y and which double a2 ‘oordionta, are called the component of the postion vetor Y=-now consider the effet tht symuitry opertions have 62 & point or potion vector (0) Rotation. In Fig. 62.5 we ahow the eft on p of» clokwine rotation by 8 (~ fn) about the direction ay i. Cy If @ isthe ro. [ection of OP on the plane which contain o and e, and ¢ the angle It makes with e, then Ue fallowing relations hold between the som (Coordinate) of tho initial vestor p (point) xy. yay sd thow of the final vetorp” (pint Px, and: dents) dee Sone Osan $x @ = dayajoon 0+ dln 8 tor reser) 29) 2a) 2a) ans (62.2) to (62.4) can bo combined together (am eqn (3.8) i Ic]. cond sind Ol fas] | -[—ane owe = ff | wan is ey ea aes cee con sn ani leche rotation of about oy of the base vector e ade, ‘moving th point slockwian i the same aa moving the Ibotatory ace t-lockwie Ege (6-5) oan be ad to define « matix D(C.) wish coresponde He a ed [ef-s leet | wan 20) De =7 tecieRoprsotions ‘The invern of D(C, a esly found to be (ce eqn (A424 snd wo avo that since 2{C,)* = D(C); the mutex D(C, orthogont ‘Ae D(C.) in ral, thin implica that i wll alo be unleary’ DXCy) Dewy. Tb apparent that D{C,)-corwponds to «clockwise rotation by De” 2s) or a ant lckwin rotation By 8, he cond ain off som—8) sint—0) DOs —|sind om of = |—vint—) east) 0 = De, (2) Retection. In Fig. $2.4 the effect on p of # rection in the plane containing ey and eon) ls shown. Cleat, m | 29) a Dew) = 2210) 7 f pop he ‘where oy i the pave containing @, and 6 ad oy isthe plane eon (lning of end {@) Inversion. The oft of inversion fon restr wl be to invert mr en eae ‘| i (4 Rotaton-rfetion. Gonsier a zotation by 0 (— 2y[a about the base vector fllowed by rection in the as face, The component ofthe point vector p (or, te coordinates ofthe point P) will be fst ‘tanaformed by the Folston, asin 0), and then thew new cone ponents (coordinates) will be teaaformed by the reetin, asin (a) Using ‘aatee notation, theo two trunaoratons ean be smb lato one ap 600 § 4918) aod we get he mee Peat meg ay [ [== = ‘|- er elm (9) ey tee lng opin, oe eo ana ea ‘wheco is tho entity mates: ‘All of the above matrices ary orthogonal ‘To summarise, we have found that the effect of any aymmetey ‘operation on a pouition vector p = ne. 0, 4465 cn been preated 7 R= Rin ratte) sie eeteey (6219 whee i te Saath a i] = Dom} 219 | a7 Aes Reprcettone ‘04 DUR) i » matic of onder time, charctrintie of R. qn (62.18) frum nouns eam srhare Dy(R) is the oloment inthe fh row and jth column of mais D4) anid =, G = 1,2, 3) a the coordinten of point oF the com ponents of a position rector. 153, Mewic pretation fr and ye [Now let us consider to specie point groupe: (1) and (2) (yy. A molecule elongng to this point group it planar trans cuttsch 1 a ll aii a H ‘The pict group ia composed of four symmetry opertions: B, Cx, doy and tho group tablo in given in Table 53.1. This table howe the ‘Sot of combining ove operation with another. ‘Following the ducunon in § 2, the matriaes whish comepond to the four symmetey operations aro vo-fers a Kei ot on-| ae {| wt nea fe ‘| ee where the base vector hare een show auch that, soinldes with Gyand ey aod eon the vy plane D{C;) han been found by replacing by =n eqn (27, Mavic aprons 79 Group tbl for ot Using matrix multiplication ae the combiniag operation, we ean ‘constewt group table for thon four mations (Table 3) og nf PS HE = Dia, [Tete apparont irom thie table hat the four matrices form «grou, soos (@) he product of any two matron tone of the four, (8) oca matrix, D(E) =, iv such that when combined with the ‘our, haves them unchanged. (@) the reociative ln hale for mates, (2) cat of the our mation has an inverse which i one ofthe Fou ke DIB) = KB), DC" = Dy, Diy Did, and Doar? = Dro) Comparison of Tables 63.1 and 6.2 shows that thay ae identical Jn strutare though the elements and combining rues re difrent) ‘sed consequently the matsix group i bomomorpie mith the pai ‘r0up; we auy that tho four matrices forth m reprtentation of a (2) @. Atmmonia isan example of « locus belonging to thie point group and i ha ix symmetry operations which olay the group, {ble introduced in Chapter 3 (Pablo 4.1), If we et up base vectors Group table fr te four matrias in ean 6-3.) Bey Be Bley Bo? Plow bay Bey Bi {2 are nt en hr‘in aoordanoe with Fig. 3.1, then the maior which comreapond to 1, Geflection in the plane containing e, std ey), Cy rotation about ‘with'o = 24/9) and GF Gotation about ey with Diet) = ICDS: Mae Rpm — 04 Group tae forthe siz matrices i og (5-38) (6-24 Duy Die) Die) BI) DIE) Bey ye Beh bey a Bi Bp | RR Be Be BS BR Bee Be | bey 3h BS) bey eh Be Ba | Be 2S Bh BS ae Be, ESE TEA he cesar "Thee six malsin frm a group for which the combining ralee matic ‘mulilintion and the group table that in Table 8:3 tbe sea x [eft conn this fr himacl). Sno this table aie i truss toTable 341, woany that thers matsce form a representation of ein apparent that we ean always get use of 33 matron, which form a tepremtation of w gn point group, by consideration Of tbe ‘ct thot the symmetry operatonr of the point group have Belton voetor. Why tie worka ie shown pctraly in Fig 5-32 forthe =~ oiCy operation of ye The rymmelzy operation Cy om the Dosti veotor p flowed Bye, on p’prodow « vestr DF which i ‘oinidental with the one produced by the opeenion e: 00. The Iatrces DXGy), Die), Diet) when sity miror whet St bing dose to the point vector Phe gene! mathematica proof tha, ytatetcy persons RS, and 7 obey the ration SR ™ 7, then the mateo ‘D(R), (3), kad D(T) ound ee above, obey the relation DsyDiey = Dir) 1a givon in Appendix A. x P0632 Rt fC a one eat mT i22 Mavis Reprnetone 1-4. suc pannus died om bab ear Tis loo posible to costret matrix representations by eonsiering the effet tat the aymmatry operations of polit group have oo one ‘tore ete of bans vector: We wil sonar owe care oth ung the ‘Gx, point group saan example: (1) tho ot of base verre ey, ey a2 ‘introduced in § 62; (2) threo aes of matully perpendisla® base ‘otra, each located af the foot of «sym pod transform yey and ey det into ef, sad Setisipate that there wil be matrices which wil ink thaws nota of base ‘ector and whieh will behave lke the symmetry operation. 1 Gy transforms ey ad et 6, tard, than we have (oe Fig. 542) Ge = nA 1/326 Ga = = amet Gevnsi= $DalGiny 6 wun we jm vas 9 e-|-vn Se 4 ‘The goneral equation linking @ and, wil be given by: Rem ei =F Daley B= 9 (42) {i important to notice thatthe way in which we have formed the ‘matein D(H) ls dierent from the way we did things whan me were ‘onsdering portion vectors fe (0217): the cmmjonents of the ‘ow Bane restr aro ue na the an of D(R) wheres, before, the ‘componente of the new pouion vector were tamd aa tho rows of & trix. This Is what implied by Uh order of the abeeripta on D in en (5:42): jk rather than 8. Nocemarly I“ a ei] dow not equal 21) | 2 ! ‘There is nothing partiulaly wubtle about what ws have dons, it simply cnrars (es the prof in Appendix 5-2) thatthe matrices 6 formed wil inded represent the point group. ‘Ane gooeral ale, equations valving coordinate oe component of postion vestor will be written in the form: Ho Bean 0d thou involving fonction (0 § 6:7) or bas rector, the frm: fin Bod hal sia Bente {in much of the mathomatios which follows fn important to boar ‘hn rae a mind.Maa Rgrcetone of tranaforen eye, and yt ay And 0 Fig. 64.2) we Sind Dee) = [3 1 of tranaorme and 6 0,6 Aad 6 (80 Fig 64.2) wo find sie = a = l(a, = -Wvanemelt Sends ona we yan o) Diet) —|—-vae 12 ‘Th reader may condrm that Dt) D(C) ~ Dia). Tes aways tre ‘hatif SH — Pav D(S), DCR) and DT) are deb a in oga (-42), ‘hen D{S)D(R) — DT); thn proved tn Appendix A.6-2, That the Imoteees foul i hia way ton th bang weotor are ential with thon ound iron sonadertion ofthe ponion vector (§ 2) a proven In Appendix A.f-."The bane recto oy ey ad ey a0 anid 0 form 8 sie fr roprosntation of «point group. {2} It we place ein of Bae vectors atthe fst of wsymmeti tepody, ‘thoes too ean produce tain rprenntation, aa ooo in Fg. 43. evieRprneationt (By the way, tho ata of bac yetor need not be parallel) For example, under Gyro have Gay = 65 = enya, (Aen ae Gam ioe Ghee a= ey (v are Gies= = (vSI2Ie a2 Gene Gre =o = “et ivsine, Gres 6 = (VAI ee ee i wes ee eat ee ce ea ee ae ee eat ct a ~ Ermey, rete a -Agnin, notice the ordering of the esbecripte in 9m (6-464). The proat {ab the DCR) comstracied in thin way form » ropreentaton of the point group isthe same asthe prot given in Appendix A.-2. Te ix Sbvious that there are» large number of diferent matie repo Seotationn which ean be found by choosing diferent acta of bass Tevtors Tho beac velo chowen ary sid to fora «bare fr the rope ‘Sotation ofthe poinegrovp. Aa with the rpmmetry operations astng ‘ons potion vector, the matrices formed hy conidring base vectors trl bo orthogonalMate panto 5 Fencin suse ‘Now we come to totally diferent method for producing mate representations os point group; s method which involve te eoneept ‘ts fonction space, The word space ese in thin content ins mathe ‘Ratio wnm and should no be confused with the more falar three ional physial space. A anctio spac i collation or fay ‘of rathomatea functions which obey cota rela. Too Palen ar = {eneralizaton of thowe which aply tothe fly of position vectors in ‘Physical apace and in onder to help in undernending them, the core ‘ponding westor rua wil be pet im wquarebracketa after each fonction ‘Consider the set of functions: ff... I thay are to bong tos anetion apace, then the flloming rues and definitions rust ho trae, (0) The adtion of any two funtion mut produce third funtion ‘hich a algo « member of the cllstion of functions, be, blonge {the fonction space [vector dition of any two postion ‘evtom p, and py produce another position Yectr Du (2) The multiplication of any of tho funtion by « number muxt rode a fonction which is alo inladed inthe collection [opr i alo a postion vector. (3) The rules in (1) and (3) can be combined together: any faction whlch oe lnea ombinaton of fu eof af) mane tlio be = member of the collection [a:b }yPy'rebs io tlmo ® postion vector), (4) The salar product of any tro functions ie defined a: Goth ~ ffthde seer intgaton ovr athe variable off (ha ol rec of to postin vectors pnd Pia P.v' = (0.0) =r cond, her the al tern the bo ator, ane 6) = Br Trusted Pa nataertsie Novia tee (0p) = aaitemitel (6) IE m of the fanetions fy fy. ae Uneasy independent (2. "Foils ahs =O ony ay = ay ty = Oi any of the other funtion of the space ean be exposed a some Hea? Maric Raprsnatne 97 ‘combination of thew n functions, (i yal pase 0 ey yo ny three non-coplanar vectors are Winery independent atid ay fottlon vector tan be expressed in tortor of them) ‘The ™ Kineasyindependant functions are sa to spon the faneton ‘space nd the rpc is aid to be n-dimensional, oj ty nd ey ‘Span physoal opace which in threedimensial) Pot another ‘rey, m i the smallest umber of functions from which Ponte to prodven alle other functions which blong te the inci space them ineaty-indepeadent function re chose och that tho wclae product uf) = yj = 1e2 my thea ‘hay are mid to be erhonormal (orthogonal and notiaained), [en ey and 0, are ant orthogonal weston) tf always posible treatm orthonormal fantion fom m lneaty independent fonctions." Purthermore, orthonormal, funetions are away inert independent and therefore, by defisition, the maxima ‘numbee of orthonormal functions in an 'wdimersional spc i 4, onal wien vein spay far ot nerd, fe maximum number of orthogonal rector inn; orthogonally ang dated by i i (BY = noite eyes ~ 0} (©) An redimensional function space ie datinad by epediying ‘tually orthogonal, normalized, linearly independent functions, (ey. ey aud deine physica opus]; they ar allel orthonormal tsi fumcion [Now lt consider two examples of « ftion space, The slations of the dierent equation te “fi, Ocecte a $2) = Be) fay form Sanction space, sic any erabiation of ‘hom ia sno elation of thw equation and therefore a metberof the collection of functions, Ln. Sires a1e = Shsan + Se tity Zorien =a Siten =a 2)-fie) tien soa a ae) afted +} —laie) + aha) +318 sac apeemaint ‘Th general slution of this equation le (2) = acon 2+8,sin 2 swhete ay and by ate atbitcary ostants. Sin con and in ate ines indepen (ay con }-xy ain = i oly equal to wao forall = is, and orthogonal (eosin «de ~ 0), the orthonormal ‘ure fron forth two-dimensional function spece st con 2/y/= sod sinaly ‘Consider the equation: Hy ~ By, where H i near operon, ya ome Sanction and called the eigen: ‘elus e courtant, I Ha the Hamiltonian oporator this equation ‘Witte the Schrodinger equation, I¢y, and yy ar tro slutons having ‘lontialsigenvelaee (Ey ~ H), chey are ant to be degenerate, Tete ‘ear tha, since Ae deind ax beng linea, Hiya pa) = Horta = Bip Baes = Blot ¥9) Hay) ~ ally, = By, = Elon) sod any linear combination of dogenerate aoltions will ali be a ‘htson of the uation. We can therefore sy that amy dogenerate nt ‘tvolutions (conmepending tan given egenvalo) of Hy = iy forme ‘oetion space If mf the solutions ae liner independent, then they ‘an be showen to bo orthonormal and aed se bale functions to die ad {hat he ry nde confit omeepon to Ry wll bo Bann faneions for a w-dmenaonal Function spac. Avan example, the thre P-orblal Py Py 204 By of Stomie pecans ace dagenerats ad orthogonal and when normalized {orm an rtbenorzal basa forthe three dimensional function space of orbital, Any porbital ean be writin, with rrpct to his basia 8 Y= aapeh byte In §5:9 wo win 4 fonction apace dafned by dorbital, The wie Corbtale of henaane are another example of « funeton sce. 14, Tramlormaton ptt (a) “ving defined» function vpn, we are ow inthe postion of being able to intreue ¢ new group, homomorphie (ace § 3-4) with «given font group, in whieh the elmenta are tnaeformation operators which porate onthe Functions of some funtion space. Wo wil donot the ‘ufos operator which sorresponds to te eymmotzy operation IB by Op. Beery Oy wil be deSoed with roupost to some perdcaat {Fancton’ space (og the wavefunetions blonging to © veh eQUrEy Macc Rprentation Jovet and they wil be wc that (0) they ciate gp mata) tat Ons 49 = Onf+0, wan where ais any number nd fand gare any two fanetions of the Frowion opm, an) (9) the correspondance betwoen R and O, retains Ube ruliploation| rulea,ag fT = SR, then Orf = Of = 040s), os) [Neccasrly there will bo unit opiator Og (ssosintad with £) wich tt 040 ¢ = 0,0 = Oe ou) ‘apd cach oparator Oy will have an inverse OF! 03104 = 0,03 = Of 0d, since Op sO4 = Op. 07! ~ Ons 00) ‘hia wotof transformation operators Oy stocinted with the 4 rmotty operations of «given pont group wil therfore have 8 group {able whichis tretarlly Ue sare aa the one Sor the point group. I the next section we show that, Cre introdues «coordinate system Ino the function spac shown forthe Or, ave san deine expicliy = tet of Oy satlafying eqns (681) to (88.0) Tho mador in warned that ‘ingethe correspondence between R and O, isso ose, aay books (incoretl) donot ditingeiah between thes, 17, hatter ot ot watrmation opr (0s) ean n-dimensional function space ie daied by the et of lineal. Independent nin fonetons fff» and fy ad if thew are anetons of thre Cartan soordinatea , 2 snd 3y then we can dine a transformation operator O, (eommeponding tothe ayrmetny ‘operation R) by the equations: (Opfei.2i 8) = Hie tnts Fab Bom (67) where «point in physi! apace with ordinate, 2 ad yin moved ‘by the symmetry apention Rt tothe oetion ot andi Tn otbor ‘words tha nem function Oy, amigas the value of he old fetSa Aa Representation yan tothe position a, and, Knowledge off. ZEEE S0 Sloe oe to tad the fem of Opis oon 8-9), Wit te “stniion, it ean be shown thatthe Oy arenas and that iC T= SR, then Of ~ Oy0y (ee Appendix A). "The fequrement that Oy, Produces function belonging to the sure tmnion ten oe (2) lb ty tho prope coe ‘st fanotion apace (oce§ 58). If thin the cag, however, wo ean writ, {oran mdimesionlfenction space defined by Uhelineary independent Deas fenetione fifa wh fo Os EDaiMy Re Vdom (Potice the order of subacipting on D), i the fonction Ogfy if Delonge to the funtion space, mast be some linear combination of that spac’ bal unelonn ‘What in of mapreme importance for, isthe fact that the wim tmatscen D(R) it en (6-2) wil tolepy i the sae faaion athe tymmetry operations: if P= SR, then DIT) ~ D(S)DAR), (we ‘Sppendis A2 9), The D(H) wo found, therfore fora an n-ne ropreeentation of both the point group and Uh group of transformation ‘operators Oy, and th fanetions fy nd faa sid to bo baa {or the repreertatio, "The operator just deaeibed wil lave the salar prodact of two fasetions af tho function space unchanged: (Oxf Oxf.) ~ Uo) ‘uch operator are mid to bo unitary and they ean ways be repre sented by unitary matsioes (ene $0). "The proof that the Oy 620 Unitary flows from considering old = [PUMP I Arm where Pin «general point with coodinato yan 2, and rpm dy dey dey 4 the volume slament at P. Now a rymmetry operation R will move P tox point P wth sordinatey (manda) ad the value element {oan equal volume slement dry = de dy dj utunted at Purthor- ‘ore. the operator Oy in dednod wach that {(2) = (Oyf\P) a0 TAP) = (O4fXe). Hence [Rg are = J ORI AE IMUOENPN Sep = foasixrnrousnen are Matic Repmaantions slnge the range of intagrationextonds ove all pointe Por P”. "Therefore, ub = nf Oxf 23) ‘hati the scalar product lf anehanged Our dfsition of Oy spplied to functions of the coordinates =, 4 ‘andy of « point in phyla! opeo, but ican be general vo apply { funeion of any muster of Yaiable, a long an we know how thos ‘aviables change tnder the aymmetry operstions, Por exatape, i re Tet X stand for» eomplate specication of the toordinate a all the ‘lectzne (oF llth muna) of ome molecule, Kwa Pat ca al {orm electrons (nucle) and if thi epaieaton becomes under the symmetry operation , thea we ean deine O, by nf) = 100, ora) where fis «function ofall the electron (mle) soordinstes, The {horeine in Appendicon AG: and 0-6 alo bold tw for thie more ‘general dtinton. ‘We have scan inthe previous mation that the definition of «art of| gis intintaly bound up with some choir of function spas, Tae redder is eautioned however, that not al fanction space can be vod to dane Oye appropriate fora piven Poldt group. For exam, the anetions co yin con zy and sin donot forms base or & ‘eprewentation of tho Wy (oymmeteietiped) point group: sl ‘0 the eoorinato intoinced bare (no ig. 623). "Tho four fnetions do dane m funoton space, since the gener fenton = Meu 4) = e008 agin 5 bajon 2, +agin a, snd addition of any two euch functions wil produce think which Telonge to Ue space a doe a number tie ay uch fanetion, However if we conser the Cy operation of Cy (elodkise rotation by ted abost then ha Cntvse Ravana aoa or, inverting yo al-vanye ey) moa$2 sate Rgenation sd electing the bai fanoton ony 6 Bod Oq{corsi) — a2, (efition of Og) 8 Kain i ° ogg) = c08 ay Using the notation f, = coy fa = sn We saar that p Cash # $ PalCa Consequently hin function space doen nt provide «basi fora rope entation of th yr point grup, 1-8, An example of demining ato) fst, pat rep sing tn Sanrio ‘Avst of five eal deobitale deine a funtion space. In epheicl polar soordinater 8, nd they coma of «common Pudi! fantion| Unee = combination of spherical harmonior YF(, $12 and sn, £1, 2, Tho combination of the fre sphere! harmonics are ‘Show wach shat the orbitals are zeal "Weis o wal known property of ephtial harmonic chat if we shit the point 8, and tors fry and 4 the roalting Y7 ‘xpreamed in term Of lnear combination of all the Y7(8 ¢) of the same I valze (m0, £1 -- i). Tho rovers it alo tr! YT, 8) (ao be expromed a «linear combination of PTW, 4, with m’ ~ 0, “Ll and therefore, 1.4) = YMG, #) (definition of 05) = a liner combination of YP(W' 4, o 0,77 = » linear combination of V7, Ott 04, = 3 AAR) 4, there dy do-daaty ral dorbitale, Tho D(R) will form a repre ‘Entation ofthe point group. Ite apparent that aa the above sap do ‘nt specty a pertcule point group. te coritals (or any oot of ‘phereal harmonica ofthe sume Flue) san be ted e the baa for 8 ‘ropremtation of any point group. With ths knowlege, we ean 10" Ne at a a a, hang the tg oat i DAE et Mac Rprmmeions ‘ue the dorbital function space to determine « representation of tho “We will define the five d-orbitale by the equations: (et, aie aa aey 4 Gal_meva, ‘whore «common constant and radial fencion have been omited (they ‘Toot norary for th purpose of oar disamion), and 2,4, ahd ‘the Cartesian coordinates of « point with repect othe bum vector ry and oy (ovo Fig. 63.1) andra the distance of the point =, x, thd zy fom the origi (conte of ua). The more atin notation im dang dy ~ da dy dg dy = dey We wil Set eomider Ube operation of dodkwine rotation by an angle 0 about th e aia and denote the ooreponding transformation fperntor and mutt by O, and (0), repestvaly. ‘The tlatons etween the enordiatar of ¢ pint before (ay 2p. and 2) and afar (Gas and a) rotation ae (on eqn (62.9) = (om Orn Oe Ba tan Oy +008 6) or taking the inverse 24 = (oo 0) (in Oa 25 = (an Os +008 Os, Ba rom og (671), wo havo el 25 38) = Aleut a = ion (in 0)" Oo +008 9 = (oon 20yaf 2?) — (a 20 (co 28) ae) (0 29) eso) ‘or, dropping the parameters thay are now the mame on oth siden of the equation): 05d, = (08 26) (ain 20 dyre Rpecrtione in the mame frhion, econ lao obtain on 1 (vn 2) d,-+(008 29 ay y= (60 8) dy (ain 8) dy O4dy = (in 0) 608 8) ae ay ‘Thus equations define th opastor Oy thi i to s8y, they aps the now funetions erated by apsiving the opirator to acinof the Sve sie ay 602) Fotoon Tetodeing the equation 040, = 3 Dall dy wos cate uns 0 0 0 J-sinz6 omte 00 0 {ene gin notion Hh nkcrpting in Dy(0)- Hane, if 6 = 28, Hun -vaz 08 Ven poo 0 0 ye vas o © 0 =vae 2 0 o 6 0 ot encase ole st van “12 0 0 0 ney=| 0 0 2 ~vap 0 © 0 va eo Siiesiile tie: Now, lt uw consider refetion i the of plane (re Pg. 6-41). We ave fom egn (3: i" «| | 3) -vare ap var ie ° oy = sive b/s vaya, 4 es 38) a 8) Ate? Aenened = 22 ie are er apemains var 0 ! vaitsi eft m7 ~ Wei —y5ftey— 3/20) 0a A 228) = der to) ae Oud, = 40, —v22 y= =V9I2 449 Pe aa ei 8) V3 ee a3) = Healt da rom thet sgeations wo obtain —1p yap vay De-| 0 0 VP aH ° ap vl 2 —vae = ‘The other eymmetry operations of @y give De) =| 0 ° ° ° VBPE aah +H Ol ae (603) eae)acc Rpeenaine 1a van oo vez ye 0 oo De=)o 0 oe van wo9) © 0 vin a ates al o1r000 pe=}00100 ws9) ooo10 he ee 538 matics apecied hy oan (5-91) ‘ve-dimeasional roprnetation of yy: the bai representation ere the sot of ie obi Tela probably not weaped the rnder's notin tha acho the above matron hn the mene nruccore, that is aay all thar non Ying ‘lomenta cera in th mae aquareMosks aang the dag! Kxroo0} oo xxo ooxxe Tooovox ‘What ie aot so obvi a Ut sie the blac structae ia dential for tory aymmetry operation, th indviual bloke themelves, wien te ‘matron, frm lwo dail rpeennation, Take, fr example, ‘the Block form mation pa 0) mem Po en ee -[%s mak am) 1) von fr oom hore D'(1), DS), D(R) aro square arrays of dimension mem and DC, DUS), DUR) are nquare array of Gmenaion msm and 0) Mac aprementins #7 representa arctangular array of sro, D(T) — D{S)DAR), than the {iatee moltpioton rule Tend to the eqoaons Di = DIHDIR) oa DO) = Dre) ‘and consequently, the matrices DR) at. and DUR) ete, form two Towordivensional representations. “Anothee feature of lose form matrices that f= matrix nin Sai (43 10) 1) ta (0 mM oO al (oon) then Seu) = delet Aya). and dat) — 0, than ther fetid) = 0 o auiay) = 0 eos) - fetid) = 0 ao We will tar to the tia of block form matrioes inthe next chapter; ‘hie foundation of mnt ofthe theorem which follow £10 Detain a rpeentatine ‘We might ote in ping that, non dat A) ~ dot(A)84(B) (ose Appendix A.tt), the dterminanta of any nt of striae which form ‘representation wil homacivon act x one-dimensional repreventation, ‘That i fT — SR and D(T) — D{S)DR) then ac 7)) = dee D1 SOUR) = aetkDESTISHK DLR), sad the group of number (or 11 mates) dat (D(R)) et. homo. ‘morphic withthe group of mateon In tia chapter we havo shown that there are very many diferent seta of matriere which behave lize the aymmetry operations of «given point group. We have constructed than so-called upreentations by fenidering the action of tho symmetry operations ons postion Yetar ‘or on any numberof bss vector. Altrnativaly, we have fund hat Wwe can find transformation operator Oy which are bomomorphic ‘Tiel he aymmetry operations and that from then we can eoneructsaute apeanatine representations By considering the actions of the Oy on functions belonging to som function pace, In this way, the portals, ae {orm buss of representation for any pont group, the ax mortal of benaene form s bai of representation forthe Dy Pt ou, aapter 1) oe ‘Our nort tak wil be to try and ongania,reduon and clamity the lethocn of representations which wo can now eat, We willy to ‘mina from dseuslon hoe which arya erain ena, equivalent tnd those which can, n = certain ano, be ‘broken down’ ine simpler (lower one) representations ‘Whore wo have now got vo and whore we are going has already Doon smmarizd in Fig 511 (om ig 832, then, fom og 2) sn $nume sau2at aa dadn, bones (asa ma Enum anes = Em Eom, eae ‘Comparing eqns (A.6-1.1) and (A\6-1.2), we have, ara pana Snasoun ADE 12) a et hth ro md eh oe i uit promi 08 sod, ocaan of th matrx malipiation rae thin aie to the deed ein BC) DIS) ‘AS, Pol tat th mugen conti insge6-4.2 (roan E44) form Spal Sa pastpe eZ Pee, EL vm OCB eer one A EOI 521k Ty EDM, Batt an casan) om, =5[$,2une)] -jams, Era E rusia, EZ [Frama baa. 1as2a) ESR — Tegn (A521) and (A822) mo be eatin a therfre pan =Zoasoam ST hot ot hia jth mae mip ao DT) = DES DR. ‘AS3. rot thet ha maviee tied rom positon vectra the same 08 ‘tse dred om eng art ba acre ste te ma$ouim, bata assy Sone ini$ Daihen $ Dane, = (S2smm [8 pam oce[S rae Habana = 2 Dae, b= Ay)100 Mai apoenains crdtassiag mberipte se frwim, bana Asn Conmaquett, the sue matrix D(R) danas though eqn (A582) (ot Son (e219) and ey hrugh eqn (A831) or efe (O43) ASA. Prot that he pertare Os re (1) Ma, (2) Semone wth the ‘Srna operon (0) Tey eto, jmber and = af hen (Oates i) ~ Hee 2) = eee) = HO gf 99 ‘his ognton must hold for any point (0) hense Og.f) = #04) aan (0) Comider wo fnetion fond gant A = fg, th CO ie 28)— flav z0) (paix 39 = 0082630) aise ised 20) (Oph) = Meuse 4) a flen a a ate tn) (Oghe s )+(Onb as 2. ‘Sloe thie oquton ol fr any point wy xy We nd Ogis+0) = (Ons) +10 (ass) oot (2) 1g nara th pointy 0 ee sy, pt oe) (5 ya em sh i ty isk ot me nt (Or keh x28) = feu ee5d (anes) (Oe 28) = ae) cas Now lt p= Opf the 5) = (Op Me 2 20) = Sle) sod thar, ging Back to 99 (AAA, (O40) — fs ‘Comparing thal aguation with og (A643), we Bae the desired rele 010%) ors. assy Mtr epoentainn 181 ‘A.55. relia meio iad hom Opteron septs Aa roi open) hn IC = BR OF O10 me oun = S0ainy, ony S rds orn Zann Or = Oh 0n(045)~ On| $7980) = EniaV014) (cision, ete provost) =Zraim(§ 9.1504) on = 3 (Zrusrvatn}s Dat = $0480) hshy.tg sax sutton rue thrive 27) = DSO, ha << aoe eS Eich eime powp malian alls n tpeanesy Spins” 2. The able now gn heeft of the tafraton operator Oy fot ‘Hoeymaeyspteone Wo te pat gop By ones hale fof2, Conder mt ht ears naa the mach af he motel BO, 80 (Se ge baw yoo sear omer tthe Sab, he Bort pit gp a (Soon Serivces! mate repetition ing Boe ral 15. onal te pla erly dal with men wailed 0 ‘practi ofthe Yet pou 6. Equivalent and reducible presentations 4, truco ‘Havsoo ape «considerable efor f erating many different mateix presentation forthe point groupe we now, irons ae it muy mo, devote an equal effort to elinneing many of them from further consideration, We dots in two ways, Tn the Srv place, we consider thowe reprsentations which ro produced by the me tunaformation operators Oy and the aaae fonction space but with dient shots of maa fenctons dewcbieg that space to be opiotet. Wr wil se that say par of mach sprain representations havo eorreeponding matcoe which ww linked by = ‘Stularity transformation (aoe §), Asi will slmaye be poble 10 {ind wt of basa functions which produce saitary matics (ewniary ripresettion), convenience dctatea that we choeee ich © aot for prodecing « reprecatation which i txploel of the other eguvalent Tn the weond plas, we etict our dactsion to thon eprventatione srhich are composed of mateiows which cannot be simulannoualy bre down (reduced) by » similarity teatnformation into block form (ol {he matics in § 6-0). Te wil befor Uae soreducile rpresenaions ‘hat (inthe next chapter) we will bo able to prove a number of fat Feaching theorem, one of the most important of which in the Unrets ‘hat the numberof now equivalont frie reprentations i eae! to the number of clase in the pot group, So tat, for exuities or {he point group ry which has thre clan, rather than dealing With fn intaite numberof zopremstations we wil have only the three ‘hich sre nonequlvalent nd treducble to worry shout, Also in the ‘ext chapter we will dow how to obtein, with the leat amount of ‘Work, the mental information eomeeniag the nonequivaeat it educble representations which sxe for any point grou, reducible representation aro insportant to the chemlat nee they provide diretly'« great dea! of information thovt the natare of rational and elctonio wavefunction (62, quran rpesenstions et un consider » particular w-imeosional function space, that ie ‘one which requires nearly Sndopendent bars anstone to apecly any106 eae and Rabcile Raprattans function belonging toi. Thee willbe many pomible diferent sta of "nearly indopondant functions which can act ta ban forthe pace Solos 2g. f we were considering the dorbital function apace, the baie Tanotons could be ast of tive rel orbitals or «se of Sve complex orbitals, the lato boing jas combinations of th former (and ioe ‘eras acd both could be tind to define any function belonging tothe ‘orbital apace, ‘Sino the g functions are « bai forthe soe, any f function oan be fen fae + om (2ote the subacipting onthe consent 4), and any 9 uneton can be ‘rites as near cotbinnton of f function uM (2) esas mtn (1 an (62 oar ove ten Stal 9a) = S(S aves) ‘and since the fe are linealy independent, chia equation EPeden ta Soe Pal = fe ‘Tho lft hand side of eqn (-2.) is the clement in the ith row and ith caluma ofthe mets formed by multiplying mate B (oompowed of {he slementa By) by matix A (compomd of the saments 4), the "ight hand sie le tho fF elament ofthe Hentity mates, hence BA=E. ‘We oan ato write t= Eate= S0o( Sten) (Suto) tanto Radu Rareenatione = Samoa Bohs and obtain ie ett ner thn manos A 5a ned ta er ib omni Baa (enay [Now let ur consider the tranaformation operntor O, (corresponding {the symmetry operation R) whichis deSned hy the equation which swethore had bane gfe 2) = Slew 2 where 2,24 td 2,2, ar th Cartesian coordinates of «point ‘fore and afar the appation of R,repectively, Let ux urns that ©, ia eonjanction with our chown function mace produc nates which repreent Oy and, be out = S.0un a0 ow, ~ 5 m00n een he senha) lfm Sh mai 28) whic opr ‘te baat the ents 7) il form he meee DUR) Thich pment Reg ie We cur may obi sents eqn toon (6-22 in the ‘following way mony (Grom eae (02.2) (On tina) (rom oan (62.0) (Grom ogn (62.9) = 5(Saerana,)a108 qian ad adel Raprtantatine Comparing this reult with eqn (82:7) and recalling the rae for the product of tres matsiana eqn (43.8), ne have nu = 3 3 asntemeg i PNR) = ADE ors A= 2% pac — papeRyR (ons) fi Di) = ADR). 29) Consequently, the marie in the bass reprosetation are rated to thee in the Basi representation ‘ein clear that change of bana for m given function space dows Hot lft the multipiaton rule i. DUSR) = DKSWwIR Cam DUSR) = B-DISRR = DIDI = DINE DUNE = DUs\DuM, ‘To eummario, the dierent sts of matron that an be used to preset the operators Oy in given space ar dient ralieatione of ‘lint i really the same representation Two reprenentatons of Pint (roup ar auiotent i mateoon and Beat foe wih DUR) = B-DIR)B for cury operation R of the point group, Convery, making the ‘me snilartytrasaformation om ll matte fs ven Fepreenttion Seequiraent to smply changing the basso the chown function space, 1.3, Anecampt of oquvaent oprsettone ‘As an oxample of equivalent reprentathne, we will consider the ‘prorbital function space, This opace may bo dosrbed Oy thee teal ‘Perbitale: ye Buby (eommonly written te Py yr.) ad el call {hin the f basis: Altmativety, wo may take three cooplee orbits is BB (Commonly written spy. Py. Pe) and we wl al this the g Inala These two ate of functions are lated hy the equations’ R= GlHv? p= teetealv? Pee —lin—PV2 tela or wep ian sd lucie Reprsntations 107 Ineo, ing the notation ofthe pevivessetoa ‘va —Hv2 6} vt v2 ol -[uve ave of a-uye -ive of ‘andi en be vert that the equation 48 — 2 ie abered. "Tho threo real porblal may be wrlion fn terme of ac of Cartesian where #7) ia fanotion ofthe radial distance r, and ie common to all, {hoe cite If O, inthe trannforation operon which sorenponds 4H, = (con Oy (sn Oe Hi = (en On, +008 Oey or taking th inverse 2) = (co (sin 9h 2 = (in e008 Oh npr sia) = pile tee) (deition of Oy) = Fos, = Fleyooe sin Ot) (eo Spee) ln ese) ” xp, = (008), Pp ety orig ot sar pe orp ba om - $ Dun where ome sin | in 0 on 8 0 os ~108 gular abet apenas ‘The matrix whlch oomreponde to D6) in the equivalent repre sectioning the g bua iss Dr D*@), given by DAO) = BDIOR — ADO fis tiv? Off ome sino | aly2 v2 of | sino om 0 Sitio tis Moin jv ys o| stint vt we | Mv? lve oppetrys etiy2 0) afuve ave olfwyys rive ol 0 0 =]o oo a2) oon (r, alternatively, we may obtain this ame matrix by considering Onis sia) = Piet) ba 12,3 and carrying ut tho sme stop forthe complex basa funtion, ‘yas wo did for the real baa Fnton® Py, Pe "fe Table 631 we sbow the matrices forall oft opertion of the ‘point group wslng both ral and complex portals ax basa fue Lone For th operations Cand Cf we have az rplace 8 by 2/3 ‘aod (5 reepoctvay in both eqn (013.1) und egh (2°32) The matrone {or tho rection operations have teen obtained inv fahion sla to that wed for the rotations, Ta carting ovt theve wep it hao bees ‘esuned that py. and slo slong the vectors 6, ey and 6, respec ‘in tho ral bal idntial to the one given in § 62) and, furter, the seeder may verify for himwelf thatthe matsiota ung the some Danis obey tho My group table (Table 3-41. umber of equivalent represntatons of « patisular rin group It a useful to choo jt ne of them an = prownype for I the other Te maken tne nt the one we chowe for tia le hae toatrioes which are unitary, since unitary tatoo ar much ear to ‘nnndle ad manipulate than aon-unitary matrioon The readet wil soul (Appendix Ag) that unitary mates defined by 2 = ‘Tart as thor are Go ways of interpreting equivalent repreeatations quran and Reduce Roprsenttions 100 ‘Byuialent representations of wong the porbtel Sanction spactt Darn okies Congr END (change of Dasis functions oF a similarity transformation on the ‘matrces) ao there are two ways of proving that i ie alwaye pow {0 And « unitary rpreetaion which n equivalent to any given sebee we choos ou bis fnctions for a patieslar faction space to be ‘orthonormal (rthogonal sad normalized) ie. Uf) =f tf, ar — Br then, nce the transformation operators ar snitary (§ 6-7), the ‘ypreentation created will conss of unitary matsiens, Tin proved i Appendix AG.1. Te should be stated that iis alwaye pore to Band ‘sn orthonormal ban acd oon way, the Behm ortogonelntion Proce in given in Appendis Ae “Alternatively, we cam prove that thar alway 4 similarity trae ‘formation which wil tnnaform simultaneouay all of the mations of @ ‘roprecatation into unitary matriees, Tina proved in Appenie A. From now on therafor lt wil be no resection to sonar, i Wa to, enly unitary repreneatatons.10sec Raprmttions 15, adc roproentninn eis convonieat at thin tage to introduce the xymbol commonly wed for s matic repratation, namely T. Dillrent representations {or « point group can then e dstngsished by = napercrpt on thie symbal for sxample the repreeetation in tof beatin 6-2 could be ymbolied by TY and tht in the g aslo by Te Tt i important to Understand that Pia not «rymbol for «wings matrix but forthe whole ‘Suppowe thet Tis an waimensional representation of « group of transformation operators Oy acting on th fonctions of an w-imeny ‘Sonal funeton space and that we have basin functions fr foes fo trith the property that the fst m (m Leone = Fovamee-nare Pompe, At some «yp dagen sheet of, wae en FERIA sro hn nt ny age Bt at a ny ol te Tt an he fF, ay ing SEocar Si of cinn, cosa: abo on FP digo ef na ane a (Ht NET anh mati 2 aaa beth a 7, cee ye EDU aan Wess eho hat hear a en iy mat = xine116 quran and Reece Rprnettons ‘Wecan prove thatthe matin D(H) ar unitary. Conde th pari Drsnrisy whet Dst Sxtpigemonistx4 Stnisio pampimtonisy et = EDI) FADE DADS A =r Fomparasrx4 2 E Dan Re. ESR = 1, thenD(S)D(R) = D(T) nes hypande ABS andance bari ‘Batis ae chaind through 9 aay arnt, they ae eg IEbe'o the unprimed ene ad wo have /(3)(R) = D'(T) Parteners, Up the Rearrangenert Theor (Appenie AS.A at Brean over tn ‘Jmmery peracgn ofthe pom roe, 00 dom SRC=) Manco rssh = x4 (NDT =rigo tu Zomantoxt teed Drarrt — Serpe re ei sty Pann asae eet SSeS aS nouperex+ 7. Inreducible representations and character tables ‘Siuce i ia the non-oquvalent imeducible representations which rofeot the emence of point grou, it upon thee which we now foc ‘cur attontion. Others which are oquivalantoroan through a siarity {transformation bo reduoed to these ao, na certain weae, supertous! tay contain a0 new information about the poi group aad we ce safely ignore them a this chapter we ftreduco theorom which in central 9 the ote swe mabe of reducible reprenetatons in tlving quantrm snechenice ‘probleus, Ths theorem in called the Great Orthogonality Pore importance. What does into abow the ‘lstionsipa which oxiat between the tatrx semente of the non: ‘cuivalet ieuciblo repreentaona. ‘Though the proof of thie ‘hoorem ie fairly complcated, it hat an elogance aod beauty. the Aisovery of which ia the remand for thovs wo taster i. Th Spl festons of tho theorem are many and include soch things asthe fact {hat the numberof lreduibe representations elms than or oq the number of suse inthe point group, and thet for = given point ‘roup the pomible dimensions of te ieduclble representations are Festioted. It als lads to formala forthe number of tines «given {Mreducbl rpresntatlon ooour ia «reducible wprewntation ‘We introduce in this chapter the word character charset is ‘the trae (eum ofthe diagonal slements of any matrix which i part ‘of «representation ofa point group. Many ofthe properties of point {group con be deduced from the. character of ite ivedwible repre ‘tatation lone rather than fos the ratios thetelvon this greatly ‘implies things, Furthernore, the Grent Orhogonalty Theoret leads {rules which allow nto sonatract tablen of characters of the i ‘ucla repreeentatons withost explsitly Knowing the mation, ‘We end thie chapter wits an example ofthe determination of the leredusiblereprexentations produced by certain baie Fanelsoe using the rules and theorems whlch we have developed. tf at this point that wo aro randy, n¢ let, to produce reales of fonsine chomleal {ater Sim the mole Knowledge ofthe plat group to whish a scleeule Delos.118 auc epesntnn ad Cerca Tt 1-2, Th rat Orthogonal Teron ‘Thin eheorm atten that if T* and I” are two nos-oguvalnt i sedacblerepreeatations with matrione (Rand D'(R) (of dimecsions ‘and n,rmpectivly for each operation of the group # then the ‘lari coment are slated by the equation EPAMDEAR) ~ nuda oy swhure 9 the onde of the group nd the sum is over all of th oper ‘ions ‘The proof ia given in Appendix A. Tee aarume that the ieducble representations ar unitary, and wo can do this without uy loa of goserality (0 § 4), then DU) = DRY = DRY sod aga (7.2.1) becomes: PMR = (le PPiam aa) or given unitary imeduaible representation I° there will be m ‘matrix slementa corresponding to each R. If the opertions sro Rom Ry Ry Re, thon thoy mates cloments of chosen send value, PRR, DAR DAR) ‘an bo considered to be the components of « gdimensionsl vector. ‘Since thre are at auok asta of matrix elements (copending Fal, 2,. mand = 1,2, m), thre wl be my such g-dimensioal ‘vectors for each inedible representation, Eg (72.2) shows tet the ‘esto from a given tnitay ireduable ropreestation are orchogonal {one another and to the Vector formed int andar way from Any ‘other non-equivalent unitary reducible representation. This i ‘eon, a the reader wil recall (Seaton 6:56), fo vetare mnt teats Pm aie tle tie, sre and to be orthogonal if (wp) ~ saitae tect orf the vetor are comple, if 1m eal teat = 0. qn (7-22) with w A oF § 25 oF F 7m iw ofthe same form ae this Bm zeszie, a ast teat 20 fa sitet 0 23) ¢ there wore thie volar Pra sieteie, crthogona top and phen i Sateaa 0 Solving thous lat two equations we gn or, aoe By oan (7-28) 481.40, we have aft = aft = 0 or xf = af = O and benoos ftro dimensional vector orthogonal to p and p’ cannot exist. BY tutetnion, thse grerally truce the asisnm number of orthogonal ‘dimensional votre ‘We therefore have the following rst: Bates, 28120 ute apnsnatins ad Chaat Tble ‘hat i: the sum over all ofthe non-equivalent iedacible eproent- ‘loon of the equate of the dseaion of tho representations Testa fr equal tothe oder of the group 9. This rt plows retitins on ‘oth the muniber and wn of the ini reprenenation of group. Tn Apponiix A7.2 we show that, in face, tha equality hol Le Troe d) = FA ‘The tase of «matrix which represents an elament of group (or an Gperation of « point group) in taled «character and le unaly ven he symbol x. 2(R) le thus the character of the operstion Rin the representation which has matrees DR), UR) = Trace( DR), ‘nd if Wo ace considering the representation I, then we write (PR) ~ Traol DAR), ‘The completo et of characters for a given reprewentation for the ‘ements of « group i ellad the chara of the reprnetaion Saracens of the tro representations introdueed in Table 6:1 are town in Table 73.1. ‘We have alrondy seen (qu (454) thatthe tee of two mateoee ‘which ave related by slaty transformation ae Mention. Since ‘Squlvalnt representations have mateioe which are Hnked. by = ‘common slaty tranformation, the charter of two equivalent Taser 7-2.1 Characters of the repraventations piven im Table 63.1 IreecbeRerseton and Chavet Taben 121 reprontations will be identioal: this i borne out by Table 7-3. ‘The vere propoiton: that ifthe characters of to representations ‘iv lotion), then the representations are mcearly equivalent, wll ‘be proved in the next section, “two operations Pd O of «point group re linked by thind ‘operation X ofthe point groap by the relation P= x98, any then P and are conjugate to each other and are nid to belong tothe ‘htne clan (on §3-8). 1 DIP), D(Q), D(X, nnd D(X) aro the ‘atric in some repreaeatatin of the point group fepresenting the ‘operations P,Q, X, and X-% then necsoarly thew mateoee tant ‘miro eqn (8) be DP) = BKX-)D(O)DEN, oan a XOX aE, DONDE = DE) = ia Due) = DY, ‘nen iP) = DXY-DIODED snd D{P) and D(Q) ar related by «smiley transformation, From {hin we sve that the shuactere of opertione Belooging to the seme ‘shee tre identicals a. p yg. ant HP) = x0), ‘This rel, to, le borne out by Tablo 7.1 whore, forthe fy poet soup F forms one clam, C, and Ci form another, and i, 9, and of "From eqn (721) (the Great Orthogonalty Theorem) we ean obtain ‘or the non-equivalent edie reproeatatione [and T™ FAM DUR = Gindabe = Wlaahe sod we eam oer andj zErum Emus Frome) = ta 1 tho lreducble reprorentatons I and ar chen to be unitary (0a tas of generality), Hn ogh (738) beaomes FLOR = 9%, 3a) inate SB be a3)122 tai apaonatins ad Character Tbe yur) = pian = Ean 209° fo onary mason. te options fn oe re Ba Re ‘een nepal PUR eo ARO 1s the components of a plimensional vector and eqn (72.4) then imple that mack vecton for diferent non eivalent tniary ‘edule rprenntations are orthogonal ‘We wil ellectively yialize the operations of the ith clas of a point group of onder hy C, and we wil symbolce the number of ‘peratons in the sth clan By g, and the numberof claoen the sroup by bso th or example, forthe ty pont group we will write = Gor Gece baa, Since the charactre of tho operations of the ame clan ae identical, swe can write eqn (7.2.8) a Zeatenvcy" ~ ate 3a) where the sum now rank oFer the diferent clue and 3*(C) ie the ‘harncer of any operation im th fh clay inthe T* irre epee Rearranging eqn (7.2.5) ae Jotreenutrcor 39) racine Raprenatinn an Career Tbien 123, abet). abe. Go) can be Interpreted as the componente of « f-limendonal vector and {ht enue rector fom the other irreducible representations wil be ‘rahogooal tof. Singe the marimem sumber af orduogonl kin ‘Slonal vectors nk, the asim numberof non-equivalent iredusble (epremtations mont also be fy 20 that if'r inthe total number of [Boreuivalntlveduible representations, then ek aan In fact we can show (Appendix A.7-3) that iti the equality which bead 7A. Mamta of esa nace roesettion seurenereaclesne Consider the sedacible representation T°": wo can write (ose ea oso * PH att oat at oat = Sar here 1° i the th iroducble eprosntation, a, i¢ the mumber of Tice I" peace in I wad ke the numberof anes in th pot [grup (the namber of imeducble reprenentations equals, om, AP- [endix'A7-3). The characters of the mations belonging to 7", 24), ie the ume ae the characters of the trses in their reduced form ‘load form ia simply the num of the diagonal lamesta of the i ‘acible matrices 7702) which occur, mulplied by the number of ‘Bice that they coeur. Consequently, we have rim arm oan for sash , whore 1'(R) i the character of R in tho 1” ireducble repromatation. fre multiply eqn (7-41) on Both siden by 478), the conjngnto ‘compos ofthe character of Ris the C" iereduatleroprventation, end Tover all operations ofthe point group, we obtain, hy uring eg aaa, permet = piece Sesh.124 duct apeamntins nd Character Tbe 42) micas rt Eenmrine = where ©, denotes any operation ofthe ith lua and g, the number of ‘peratonn inthe sth sla, Rg (7-4) inom extrmely eel forms, trhich ean be ealy applied (provided the spproprite characte are Tabi), fr determining the number of en 2, that the Tie ‘edactle presentation oscars i the *™ reduablereprestatlon. ‘Wo are now in« pion to show that two sypreentations with a one-one comeponience in character foreach operation, are ‘eceasriy equivalent (ace $7.3). If wo consider tro dierent now ‘Siuivalot lreoise representations then, since tho characters are ‘rthogenal eqn (7-34), there caanat be one-to-one corespondence Ife consider tvo diferent redusble representations T+ and I then, by ea (743), A he cbaractern ace the same, the reduction wil aso ‘be tho ste ati the member of tine Tovar in T* (a) wily the formula be the entne ae the mniber of tmee T* occur a T°. The {daced tion can therefore be Broopht to the same form hy re ‘rdering the basa fonctions of ether [or T. Tho red tairicos (ie therefore sqivalent and noteamly 1 and [from whence the ‘eluced ations came (via a mlarty teneformation) most slso be ‘Ssivaloat, Hone, we have proved our propontion, 115, Graco rrebctiiy “From ego (7-41) and (7.2.4) we can diaover a simple condition for 1 ropmeontation to be iveductbie.Comaider the representation T=, We i= Secu eon sod multiplying both sides by 71(R)* and summing ove all the oper- ‘Mione of the plat group, we obtain primey ~z[Soren] Seen]? = Ebealgeomeen| ieee trouble apesnatins and hare Tier 125 ‘Now, if Ti freduibo napetion of eqn (75.1) shows that all he 1 ar tro excopt for ono Which I uly, this one corresponding to the Dlrcular ieducible representation which Se iatial mith [80 I Tin ireicbl, the sarnctar sour ley Frum —9 ‘wbich give «simple tat of whether 1-6, The raacon of radeon ‘When we come to apply the rate we have ao far dicovered to quantam meshasioal situations, we wil find that the aplication ‘iualyrovevessround the rutin of ome rectle representation {or the point group concerned, We have alrudy seen how to find out ‘which imeucble representations sppear in the edaoton af «reducible ‘opreentation, namely if we mete Pa Sar aot Eee ~ 74 SoanCae iC [Now we ask the parallel quostion—what isthe new choice of basi Tanetions forthe function space (the one which produced T™) which ‘will produce matic in thee fly reduced fora! Once again we aro Teoking at the oppnie side ofthe din whos two faces era siaiaity ‘formation snd » change of basin factions, To answer the question, ‘wo have posed, we will invoke the Grost Orthogonalty ‘orm and ‘cary outs otaln amount of vrightforward sgebre, ‘Seppone that we have found f diferent fonction space for «given point group where Fis the mmber of elaaen or inedible ripe ‘entation for the point group, and seppone that each function space ‘Provides the bass functions for one ofthe Feedba representations. If the dimension of the wh ievihn roprematation iam, ther wil bo my orthonormal basis fnotions desing the wth function space ‘We will rite the rte of baie fnetions a FS PUB ‘where the anprecrptonf shows the function space to which it blongs, By definition, thee functions must obey an equation of Une nme orm126 duce apsmatnt an hrc Tae seen (672), that, o~ Smee IIE 7-61) {poup. Sine we wil choo the bal funciona bo ohonoral, the ‘Eucoss DR) willbe unitary ow 54). ow lt un mulpy eqn (081) by DG(AY* and som overall R romeqr@2a)webere Foun = E x Dia Dims tlt Fanon = im enbalt a. ‘and, fe dice «new operator Ps by Pr =F DUR, ora) eal PUG = ln adel on) [Phin am operator which a a deft near combination ofthe tranafor {nation operators Op with coticenta which ar unt lo the matecce {Tita (lor seanona which will be ler later) called «projection porate Ip 9nd g ~ joegn (7-64) Booomen Pui = ola 68) sod Van Vieck han called thin equation the baia funtion generating ‘Sachin, snes from one Bai fnetonf7 the other cane generated ‘Parthermore, we can create another projection opertor P” bythe raha $ Frm, aso sd hence, using ogn (78.4), Pn Siasdaft Ezounro, a OO ae ee aan SHH EYE OfeaeulS cia eue ts ras) Any function belonging tothe function space which has boon wd to prod I” oan neoomarly be written ta some Hnear combination of lull apesnations ed Charace Tb 127 GioBis of, a0 wo will denote auch « general fanction By fog, Then from eqn (8.7) iw A + we abla, Pia = Plesiseste sf) it Tit oasy sod tom ogn itn = + ei ee ae) We now se why Pin alod projection operator; it snnhiato any function which dow not belong tothe uth pace and project ov ad ‘lilies by g/m) any fonoton which doce Tat us now sotaider the m dimenalonal rile repreventation 18 ‘which Is produced fFom the fanction space whose basi funtons are etfs ad Io un sarume that in the Fedacion of T™ no fe ‘die oprematation ofthe point group eoctre more than eace Sy ooking wt redaction noe a hago a Po Pao A Rs Pgs So BtoB hore ie the aumber of imeducibo representations, Prom this it follows that it must be powriblo to expres the g funetona a4 linear ‘combinations ofall of the f functions ‘The functions /:(¢ = 1,2,..m) mart be functions which belong to ‘tho apace which prodacea I since they are wily near combinntons ‘ofthe baa functions which dein that space, If wa chose one ofthe Irmedueble zepraeatetioan, aay", and apply” the coreeponding (en Since Pip «linear combination of the operator Oy and Oy in & ‘know neat combintion of gy tsar Py mut ale Be ines128d Rapomtatins od Characte Tbe bination of 9, = eB rom eqn (74.1) me can obtain linear Combination fs which are proportional to functions? which belong {a T* end i we apply Peto cach p fonction in turn, we get linet ‘cmbinations of ¢'s which belong to T* and from which we cea nd my ‘hich ae linearly indepondoot and, io wih, orthonormal “Hence we havea method of finding buss functions which bloog ¢0 4 given imduablo ropreentation if we aro given ome fonction ‘pace which produces» reduclblo represntation. Notice that in ‘ition to the Og, she conserastion of P (eqn (7.68) requires ealy ‘the knoeedge ofthe character of tho I reprewntation TET cour, for example, twice nT then fee fboftt Roth sod /! and ff" ao both fonctions belonging to I and ate bothlinear Combinations of ff fr, thay dio wlly in the otis ey, i nn Sea wekan + ‘cr method ia not capble of wprating thee two functions; we will Shvaye gets combination P0,~ ohnaeaf So tha ina cs ke thie wo wil btn mixta f toate ff Sloe cnt of wah clone woud be efoon odode foneon space leading to 1 "The wefunoan of the rents of thi section willbe exemplind by ‘the problem fm $7 77 Chretien ad tic cotton Since we wil entinually be roqueing the charactors of the isdusible reprentations of the point groupe, it 4 convenient to pot. thom together in table known ae character ible, Inthe character table of point group each row rafrs to particular irvdactble representation ‘od, sows the characters of operations of the sine clan re identical, tly 8 single entry 2°(C) in mado forall the operations of « givea ‘lat. "Thocolamane are ed by a rpresntativeelemoct ftom enc ‘lee prevedod by the number of commas or operations i tet cane gy or example, the ,, point group has three claws (and neceesrly ‘thre irraduible representations) and ita character table ie shown It duct apasnains and CharcaTbie 128 The character lable for (he Sy poi group! fel EtG toe ‘Keon equa ‘able 727.1. The fest row corrgponds to T* in Table 5.1 and the late row to T* in that table (We have not previouly dacumed the ‘Biddle representation) The headings of the columns in Table 77.1 ‘tro, 20, an 30, and they imply tho Meni opertion& (one ela), ‘the to rolatons Cy and f (anoeer la), and the three rections ff, of and of (a tnd laa. ‘Theainen ofthe thre repreentations (dy dy and wl be dacanod later ei cnay to Shook that the characters in Table 77.1 antiiy the orthogonality relationship (eqn (7.38) decane eeepc 4 etl ono th of Tagua ten genemprtmtn HRI) = 9, cc i ia Ce ieee ea Thr an atnganly rato een te amas Peper Eeccoetey = oot, on sod the reader may confirm for imuelf that thin equation too 6 ‘Mee. The poof of ega (77.1) i pat ofthe proof Ut the mamber ‘of ireducble representations is equal to the mumber of elasson of point group (oe sy (A310)130 tafe Raprsetton an CarctaTai ‘Though the character tables for al the important point groupe are radily available one fr exumple, Appendix I at the end of this ook), maken m convenient nommary of our nla to ace ow the {bee can normaly be deduced wihowt explicit knowledge of the ‘matrices thomenvos, Tho fllowing four ul ean ba wae: (2) Tho cum of tho square of the dimensions of the iredacble epreatations sequal to the order of the point group, ines (the proof of thie ie given in Appendix A.7-2) Since the Wentty operation ix always roprennt by the unit orient mate, Cy Sats Sewy-s Se he min: fom odin! tty symmetric iredecile reprenntation of any Done grap, ie ie Satomary to put the coreponding charactor in the ft row and w 24) = (2) The number of ieeducilo reprsotations r is equal to the nuaber of lane E: the prof ofthis x given in Appndls A, (@) The row mint ety Spartenrer 0 (4) The column mt stify Eetearcir = wate From thewe four rules i x omy, for example, to contract Table 4.2.1 There ao thre clas for Ey and therefore thee irmuctbia ‘epreentations Tho only three nurtures whos nguaen aid upto ein (tho order of the group are 1, and 2. We therfore mmeditaly have fel EG oy Si i ImedecbeRerseon and Charetar Toten 131 nd have only to determine 2 and Brom rule (3) we have 142043 =0 ot Baca =o Ayaayae oo ‘There are soveral general metode for calculating the character of tho Inmcusible representations which ary more rytematic than the ‘method we have given. Tir drawback, however Ut they inva Jong and comaplon ealaltions and ae oly fatbe when tet made ‘of high speed computer (00 for exampl, Johe D. Dison, Numarvche ‘Mathenath 10, 440 (1907), Furthermore, Eako Hiker ha dvcribed sw Ghnery forthe eonetretion ofthe nesdoible rpeeentatons of the {nite group from thir sharecters and though complicated ean be conventenly programmed fr « computa (oo, International journal of (Peau chemistry VI, 025, (1073) Tse rondae who iterated in the ‘art that computary can piay in group theory la recommended to read ‘he ar by J.J. Cannon tn the Commutation of the aasciation Jor sompoting machinery 13,2 (190), aioe cecata plogenreniromaerarqray UN error egecetetng angry ane a eniaee r poena eeeee ert a eee poem pores opel g Scere et eae eee eee ae eee ater tng pe roar lp See rr ete a ye Sate etecegae tees ae acetate eae oi Rhomararitte a deat Yaris are ars Ber Ronee eee Raa eS ReneS eee152 nou Raponaions an Character Tbe haractary ofall thre G, operations are +1 aze labeled, while the ‘ther ove dintnsooal sepmeentathon ate labled 5. Fot yy the ‘harnotar of Sue dilaraines the label of the ene-dimonstonal rpre- ‘Two dimensional iredusible rypremntations aro labeled, which should not be confed wth the identity elamet o the Meusty matrix. "Thre chmensioal iveducble repromntatios can be labeled iter or Py unvally Pie wad in letrone problema and in whrtionl Pipe pent group containe the operation of invasion, » aubseipt ¢ trom the Getoa ward grade) ot (ftom the German word gerade) {1 ddd to te aba acourding t whether the charactor of postive tr negative repoctivay. "Te inverion operation i always represented by 1 or —1 timer the identity mates: hence the ebaactr iy sither "Dry on my wher my ie tho dinension of the reprematation. Pobnt rope which contain fare fx 0 oven, Dy (meen) Pu (9 098), 8 {End 2. and thee point groape ae often writen us € 04 (woven), Bro tmoven), 3,04; (n odd), C84, and € ano, rnpetively (he ‘Foret ance ihe) contain al the operations (R) of plus all Cows ow can bain by combining each Rmith Le. RD). Thro are twice ‘Stoany ctntnin 9%, anim 9 and therfore twicomwmany ireduibls ‘oprewstations, Thun for euch iredueble ropreentation of # there ‘rile repeseied by sor 1 fies an detey marie a tat there {re twice ws many iredusble represents in 8 @ 6, a In & For T= AR) = 28). PGR) = 218) aaah PAR) ~ 200), exit = 24) (Gora proof of thane equations, s0e Appeadix € of Schonland’ bool ‘Mouton symmetry). if the punt group has oy operation but no # operation (groups ta sd ng with odd) the Ibeln re primed or double pritned sesording to whether the charecter of teepeativly wll be represented ty #1 op 1 ines an entity mat eel that there (Te twise un mang itvoduibe reprnentatioa in 994, arin 9. For T™ rm = 200, vie) ~ 70) deci Repent and Charest Ties 133 al ruy= ra, Fah) = 2, 1000 can write point group either an $0, oF OM, (6 the frmee takes prootent lst! ebay aed th so i the sowoquvalnt ieee roprcntatlons which ar bet itinguabed by the foregoing rues. Exeopt forthe fat that the toually symmeteic rpreestation (one-ditetaional wit mates) fs ‘numbered and ln fs, the numbering arbiry nad the rode in rfered to Appendix Tor Mullen’ pot forth internationally “fe cne-dimeaioal representation has complex charactors, ‘hen there snat be another equally accopable representation with the starters ye", since for «one-dimensional repens tion the tnractr ofan persion equla he uingle mate clean rpreeang operation. Tow pals are snslly bracketed together nd Inbal In fact quito often the rudvctiog which produssa the pat of ‘eda represnttion i nat crre out, sinc no ssl formation {is guined by ie and anyway the two alway ocar together, The eo nite pe rsa x wal an (= are tha cornoition, Beene thee grouse an nite amber of element {he theorems we have given do Sot apply and ether mar caborsto ‘methods are weeded ond thereto representation € te Fire of rotations C(, Cl) though equal and oppite tigen, agi fe owls ed ah ane tie tion 9, belong to one case Ths pint grou haa wo ene-dimen Sona! ree Topnsiatioe sadam Wine mune of ree Atimensonal ones. To Maliken' notation theee would. be label 4undy By 2y- but a diferent notation, ung Grek letters ad ‘rll vad developed in warty spetourote work, swell ployed ‘The charctr tale for Way a shown in Table 78 90) Taste 7-81 (Character table fr agIn ener to demonstrate somo of th conslunons ofthis chapter, wo which reduce ope ‘al dorbials or thai shown (ee alo Fig. 361) 0 well ae Our cholo of 3, and 200 {thas cscs entablnice the onetation of the p. and dorbital) Ia ‘Table 11 the cormesponding character table ie given i fall. agent ‘To find tho inedacbleropesetations which can be produced from ‘he orbitals wo neod the charactrs 2~(R) andthe effet of Oy 00 the ‘nttala, Taking the lat polnt Sit, we And O,g forall Rof and B= Due Pe-Pe i Se, yd athe route ar given ia Tblo'7-2.2. ‘We have cared oat this Lind of atop btor (on § 6-0) and for thin Dertcaas point group and aais choice, the prooan in particularly mpl, for examplo we bare nee Qe dem Qen ae act ‘Tanta 1-024 Carat tal for Sh Tanne 1.0.2 {he fonctions Og forthe ranormatin peat128 trade Repenettons an Chart Toon snd if we consider O,,, under the Cy operation we have (ac gn (easy or | ee | v}-|-1 0 oly) o |yf=-|r 0 olly' el Too altel = fel fo 0 2 Ocpules¥s2) = pfa.y.2) thom the dition of) or sinc the coordinate re now the same on bath ado ofthe equation. ce = ~ Pe Alto, wang = aight diferent bet nonetheoa straight-forward way, sohwre ‘From Table 7.02 and wing eg (67.2) wo can fad the diagoal setoete ofthe matsone which repose the Sq pint group is the orbital aan and inthe orbital basi, Brom thene clementa We gt {he charactors of two reducible reprentation; they are abown In ‘Table 1-03. By opsying eam (7-42), ao Breer wohere i Pe (pans) = Peo DR Po (Adal = Moree ror So that we know tht ther are p-orbitleo combinations of p-obitala ‘whi form stain forthe iroducblerepresatations Pand P¥and ‘Toriale or combinations of d-obital,whish form = basin for the lnvedle repreentations P*“, Py, Pt and Tanue 1-03 [Th charac ofthe edie reprenaions sing ‘pert ond orale128 tnnal apenas od Character Tien [oft out which obitale or combinations of eras produce ish spovntation, we Mae oe athe ojnion operas P Kenednom gag a Pogo, 2s sppying thi opertr tench of thoi in tu we poet ot ‘Socios longing f= In Tati 94 colon topes aes here of sping Pe fo ec rede ainaeotive of applying the ten projection operator forthe a point group tothe Sigh fncion, The rts are found by einply combang Ting snd 7-02, Recalling that fon (70.11), Prem lin Teo that py and ps (or py and p) belong to Mand form bai for {gt two-dimensional ineduible eprsetaton; P(r p.) belonge to Déws dy to Pr dy to Dm; dy and form w ba fortes twosdioes onal repreentaton D"; and dy booage to Te Arnal ‘AZ. Thu Great Onhopenaity Thora ‘Te prove this theorem we fit hare to pore two theorem (ation sister unas) oscerig thn ttre ih eau il a ‘ats fa ireduhis rpm, Wel al thse oat (1) Phere 1 AMES oe ‘Weave to show therefore that if ni ni ADR) = DRA fora R any dain apenas and CarctrTabion 138 so th DUR) aerate ten Am A, whens 4a onan Ln ja oo aafeae ‘lst we dlagonaze the commuting matin A byw ute a Dm — DHX (nk DR) 20 (R) ~ XR AL ANE Sesnmax Dax = EDA ADRK. Hono, if DIR) = ADKR), Dumye—201) = 0 snd 2 and DR) commute Dime — 218) Seam Zzam none te tes sot 7 Zy=0 for BH ‘arto Dis = BDA) fe 2 cara) Disb 29 FO (onader on apc diagonal eaont of Z bythe it. {roma ator, hen ya (AF 2) shows hak i DyR =O F— BB Bik) =9 622.3000 the rnaformatin X.DUR)E. Bet we stat Unt the.) ary tbe ‘Sn hrf, oanot be dierent fom the ater diagonal ts BY ‘Season we od, therfore tha il he diagonal lento the daguen!40 teu Rpenntatios and hare Tie Aa xa. (8) Thorn 11 ‘Tis thorem states tha i for same group ther ago two diferent i reduce repeats Yo and Fri mats Dy aol SR) Bees San rpms an renga nt sah ADR) DXRA forall, Co ay A my — ny ter de) 60 an the two sepreentatone se ‘gata or cho A he ll at, case fa, ian A= “Withat Na of gicerty we ease thet the D*(R) and DR) are sntary aod myc Then AD) = DARA fra canis) sod aking aja (0 og (43.18) Dima = aR! sd ie D2) ane DU) ace unitary DRA = ATTIC) oe. (682) ‘and mliplyng both siden of in egution by 4, we et ADA = ANU, ane Steiger a by lion, operations of th groupe (4713) mpi ADR) = DUH A sd maiplying by 4" weet: ADR) AI = DRAM ans Comparag gue (A714) and (A748) we obtain AA DR = DIAM, Aa ae ane "Thon, by Toren I ImaucneReprsetaton sod Chavet Taies 144 aaa) = dean) deepest) = 2° oe Appendix AA) 162.40, then deta) #0 ane Abe an Snr and we can write Dim A (tl) sod the two sepemeatatnn are aguas, 1F2.= 0, thn 44" = Gand vaya ed ASO ABs ce pina ra Sa a th den") = {401(B)} sd =a metre wm taontmmenenione eg finde a Pik lars Pum nt ea pont ses eee SEES res sarvaie Ca An FDISK arin ge isan wbiy mais a thevumaton over ee pation AD)~ DRA all)(2 lade Raprnattan and Carcta Tabi sod hence A =H (oe Theorem 1). We do thie thregh the flowing stops Daa = Dm FSIS) = 3 Pens xDIs.DEr DURE = [zamsxo.es)]om = [panxor som = abe, FE nsorsrss ~ habs F Pats Das) = rab Stung (J and summing ove we obtain FE whe = § [EPaaennats} Frais") Fah = Fim Pbuy (9 number ofalaments in) Jan = ag = a maui Rape nde (A228) bomen FPalSPaf5) = Wh ba tae opr FROME = Une, 4) (0 Core th ma “aa potro (Four 9 vith dimensions gy un'n, nod 2° aay arlteny tee Mates hata ite Tran Prana POMBO) =F rmmaxpsoeiom ~ [pownxocasi}om = fpeineor nm (ig ahr aro ps (is YS 7 ae nb now-uet Thre rue Chance Table 1 aSembing gee 9) ZPRUOLARY = he Oe (ATLAY) Whe pro P=" te mae meta) we tae age (A719) Sod when fy 7 wo have qe (ATI A0) Ege (ATL 1) eeprom the ‘Gra Ordgsy Torn 22, ret nt "The proc tha hmm ofthe guar of tha deans of ha recible preston egal to toe ena the group ke espa ate, EERE gl vpn, he Cataad rent144 ius Rprsnttion ad Character Tble (1) he opt represen a oer ery Giz 6 ie Pus ert the mates of the eglarrprtetation othe opratin Rs forme spare iy eng oy eyo oer opts vay = 10 lee Une 545) 9 nad hat 6 AE thee ZR) = sehr Bi pete atch ginal ha iy ee PRR) = PRIOR) wrsinn, = Sverng Den (ar2a) ‘rom the way we have et up the mies, wo Koy that, mrinmy [tf RRA RR an) Se Rona Ait mR, R, lot RRR, (area wary rR ~ By the Heurangeent Thor (Appendix 41) thor wil ony be ooo {owt or whieh A= Ry ant nly oe vale for het y= Ry ‘The ta over in eqn (7.24) wil ash unos fr une sing Fle (oak Dye) aid D3) te dealinasnny meee an ist one, eee SR MPR) = RM BPR Ry ln whieh at the een wil ual ity. 80 we lo ie RR, ARR, eh when compared with om (A7-23) shows that (A723) i trae Teshans ths min doors mrpectation te gay Semeaorny = (2) The erate Phere "This theorem later thatthe numberof times each (reduce repre spines cine rpc Selo, SEE gp nine ponedty ong eae 0-43) Woke aes) it AB, mR) 0, tht i Spe spam -rn, Battles ane (9) Pr tat By se construction the dimeonon of Tt eal tothe crder of the soup 7 but mural bo elt to in ofthe demons of al the ‘edu repremataicn to hie can be ren the Fame za ‘4.7, ek thre acon "This prot git sompler snd wo wil fit mummarie the defitions (etm of which hare pened fot, seo 8-0) which aw Lo be snd, = nay oper nthe in sas Ge Uma the ey operation‘He Inada Reprnetton and CharetTaben = 4 gon in th stn nvr fh pectin i the operation of th math a Hn dinco ef the penton bea das Kz = the sum of tha inversen of the operations of the ith clas ‘he proof of b = + has ¢wo parts of which the Kew ia to prove that KK ‘nol componed of pas Sae (0 ry eR = Se "To understand what iin we wa to prone, consider the pymmetr ipod rn goup ty for whish ar hic saws an Seine ce am 9K ary SHCPEOHY EY Opt 4 C24E = 8430.40 sp nome that Uo prodstof any two ann produce ina combination Genuider the transformation R-1C,R for lt operations of the ih case Sesh esas {aloe ix number tothe number in te it la Sc ean Shtewsesararaa neue Representations and Charcte Tate 147 ‘Aa ont. emery fr pion tn ae hry he ea am KR K, on, wot hat moat, bo sme iva coiaation fhe B= boRP BRE cars, ‘thse RI snd AF a wo Operations of he mek lacoste etch sd a nn bare positive integer new the tase W when (A792) to tana the hand ie of qn AT3i}, meget ORR RKRRKR laa one R ofthe grosp) (A732) (sin GR = ote) (A793. go bai ARP URE Eo mba. snd ncaa = b By gern tie rnlt we bo tat every operation Sa Sh ctr sq Ryan, Rtn KK, Sak ras) tr ott pie nae (2) Pref tat b= We wil dene he mati 8 =Sray ary ee cee enees ell lag in La “ion ~Soumm (mera) Errore148 trace Representations ad Chant Tbie (ote that ZU) = DUR oe (5.2) a talons Drm) ay = AID “ATITRL Lag pee mene an we Tier 1 CArpnte a= ae (rsa) gg AB oetnt mates Bay (A790 pln thatthe actors = a6) = Bm, =r = ge ara re) rom ean (AT) (ne Pat (1) we gt by sng the I repromntaton, aca; $ mary ota = $$ oad Suku sa Zout sd rom og (A730) sxiGnosrc) 3, oat) Pe) re) 2 = POE tae Co. ran yd = ne ha oven santCar sen eee ee So eater eee eons wok rentey=Zeangeeries —«aras) a(R) (ES regular ropremntation) ah) ee) Seve (A730 208 st ago 720, soSqeoney-(2 448 Spear) ~ inde te rue ern si) =F i ae Seen ~ in) 4 Ths ts een so at § recent igen sin Re eee ade ee oe ata ope sesticns H Haw bave tay chs (gn 49) har Sree white ae iaatis fepreeetation T of 3g. Using projection operators God the ononrmal SEED Ramco wisn aaee Aco eA 14 Sh at rnc yt rion ram of gn (8150 edie Rprsetnton and CharatTabor ‘8, Representations and quantum mechanics 1, orn Iw this chapter we introduse the Schrodinger equation; this equation in fundatnental call epplcatione of quantuss technic to chontoal ‘robles. Hor molecule of emia! tern i ean eqoution whichis ‘omdinly dificult to solve and any pombe siptitonions dv to the \yarmetay ofthe apetrn cooenened are very wahowte, We are chlo 0 {ateodco eymmetry, and thereby the rele ofthe previous chapters, by proving one glo but immensely valuable fat: th tranformation ‘perstors Oy commute with the Hamiltonian operator, 36. Tt ie by ‘ie ube thread that we can then deduce some ofthe propetin of ‘the solutions of the Schiingerequatlon without oven raving ie ‘Varthr, we wl ind in this chapter that wavefunctions (macloas of clostronio) mut be fupelions which fora baor forthe ireducie ‘spreeatations of tho point group to whieh the moloue belongs, With {Rloknowledge we are lato determine which incegal over nlecdae srevefunotions are necamerly toro and thn ture (nest chp) lad {e wall known epetroecopic election rules £2, Teint Hoinian opto 0 ‘Asie fom mst and quantum seteiyonn ects « ge molec in fre spac holly dented by the Sebring sevaton oe = BY, 2 where 2, the Hamiltooia, i an operstor defined by eta quanta ‘chanical alg and which can be datermined ely rom » knowledge tie numberof electrons and muse and the charges and eauen ‘ho mucll¥; the total wavetunetion, ie function ofthe coordinate of the cloctront end nuclei deinen through further quantom mechanical fulag ll the propartes of the molecle. ir constant wo i the total orgy of the molecule. Ean (82:1 ie sins to ag (1) and B and ‘Ye aaled the eigenvslnon and eigenfunctions of the Schrodinger suntion. The equation solved by finding factions such tht when ey are acted upon by 2 the functions are simply regenerated ‘msltipied by » comtant, For moleulas containing more than tree utile, olution of Selrodingor equation ino way matter (Deon of152 pnts nd ant Mechs ‘aathematical dicate and oneha to rrt to approximate methods, "The render might noto that if one i intrested in yetoma which sre ‘hanging with tie, then ego (21) taken wlighty dierent form: the timedependant Selebdingersquation and the eigenfunctions of this ‘uation are fants of time “One may of snplifying eqn (821) ito wae the Born-Oppentalmee ‘approximation; we will ot go into the detalla ofthis approsiation Dot belly nate the reulte which come from ita appintion; thew are: shore explsitly yu ta fonction of the exorlnata of the slectrone eae ad you's ftnction of the coordinates of the mule alone. TE {Fe comider © moloala with m letrone aod A much, wo oun lot, Zjrbotiee the cllestion of slactronie coordinaten x20" of SERIE SP a and Kya, symbolie the collection of 3V mucins Ctordinuiog (or aiplacementa ofthe muse from certain equlbriam postions) ese, esa Eg, €2",2; w that Ye = Wala Kad Yone = Youlae) ‘and we ref to X08 the electrons configuration ad Xe at the ‘mle cotiurstin, in the Bora-Oppenbeimer approximation yy and ype ate datermined by two noparate equations, an electron equation Haya = Baya 2 nda mucloar equation ies — Byam ea here Ha = Tat Yu ory ‘Ta ~ eestroniehinete energy operator 29 = Laplacian operator forthe th dectron x aa oon apeanains od Onn Macance 182 = Tat Vane wean ‘Tha — tedker hintiowoorgy operstor Vase = Fal ne)-+8lee ropaaon arma 1 = Laplacian operator fr the sth mud AO I aie + ayn + ae 20) awntially Chaptr 9 i concerned with the aolation of Ube nuclear ‘equation (eqn (#23) whichinvalventhe eject molealar vibrations, ‘Sh Chaptor 10 ala with eaamplon of the soltion of the electronic ‘cquation (ogn (6:23), The reader wil have observed that the eigen "Ba which oscar Proving the fil toal meleeuar energy "Prom our pint of wow the mow gnonnt thing about the Hats tonian eperetrn Hoy aed Hin, in that they both commute with the ‘persone Oye we my that Had Has ar variant under al «jm ‘iat taneformation apertons ofthe pent group af the Mcleetas Exowerk OgttafiXu) = HaOef Kad (210) Optana( ae) = Hons OS and 2a) where U4) aod fa) age Snetons of the electronic and nusloar Soordinates wpectvely. We can prove the trth of eqns (82.10) and (5211 by bowing that gta fa) = THOafi%e) nT anf Ean) ~ TonsOaf an) 232) 13) Oahu) — Vaal Ke 219 OWMrnf Kane) = Varta Eee) (25) snd tia done a Appendix A "Now sonsder the staatlon when Chere are dageerateylations to the equaton Hy = By e219154 reertains nd ann chair (his uation stand fr ether ogn (6-22 or (2.3) and what follows fe 00d for oth eletronis and naclear aan). Wo eve = B9i Hy = Bei snd since H i linear operator (20 §22) any linear combination of May byt) = Buon byt) “Therefore, ll the solations with =, frm «fancion space atocl- tod withthe enargy B, (one § 8:8) and i'm, of thom yr ys VE, {re inary independent the space wil be Ewe can show that dhe functions Opy fall andj = 1, 2.4m) sao Delong tothe function space for nergy Ry Dan we can rice oi S0uM Fm LD 0d the yj wil frm a bara ora repreentation (with maser D'UR) ofthe point group whowe operations are RI la eay to prove this ia the flowing way HOqy}) = Ox) (Hf and O, commute) = On. = Bio ‘and therfore Oy a sltion of eon (62.16) with an igenrale ‘tnt comequenly « member ofthe funtion space; ican therefors ‘be writen in he form of aga (62.17), Wa ay thatthe inary inden dint degenerate wevefunctions for energy love frm a bain ortho epreentation T ‘We aarue that all the dagenerate wavefonotionssaocated with B, san be obtained by all the Oy acting ons given wavefunction; this lknown aa normal degenersay. Any’ degenerete wavefunctions which ‘cannot be cbtained in thia way we tonsder vo be acidetlly degener- ‘tae. wecdentaldagonercy hae no obvious origin in the pjametry tthe nytem: Barring auch ao acidental degenemcy, the separa ‘one preduced by eqn (6217) wil be iredadble since no smaller ‘matccen could expr the mont general tusaformation, Wo ea thik St aecdental dageneracy asthe numerical coincidence of « pomber of ‘ier energy loveln, cach with ia own iedacble repremntation. ‘epeertetins nd Gunes Machin 105 (, pat another way if the mation in ogn (62.17) ar not ere ‘hea the degeneracy deemed to be acidentalt ‘Since we Know all the fredaibe representations of pit group, swe can tal Toe sbout the posible solutions to ogn (82.1), without ‘Sually solving For example for ammonia which belongs to they point group. we knew from Tuble 7-71 tht is elacteonie wd nuden? Tevedunctions mie ll into the following tee extaporin hone hich are on degenerate and totally aymmetee (unchanged by ll the transformation operators O,), they wl belong tothe fo epreeentation ‘hove which are con-dogecrate, unchanged By Oc, but which ‘change gn under O, they wil belong to Tt: Daim which ae doubif degenerate and unde both Oc, std Oy, each ‘eveluncion of «pair prodeom # linear combination of tact and Ie parner they wil Belong to T™ 13, bit poe rpsettions within 009 [ie alwaya poutio to form anew, and in general educible, epre- septation T of «given pat group from any to given representations [and 1" ofthe group. Tia i dono by forming » new function space for which the basi fnetions are all pombe products ofthe Beals funcionn of T* and "Lat the Baia Snetons of T* and I” be fill aa Filio Li, respectively, where n, and n, are the dimensions of 1* and I”, Then the basi foncions for Pil be fff (@— He mj — les mh ‘We wil put thse fnctions i what i aed dionary ender Mh. nit 2 IRs boon = fils ee ‘SSince "Pon earner Pea ni oy ano aeaaa for 4 np tation which we will aymboice by rep oan IO i alo the dirt product (or Krocer product) ofthe ree seotationa Mand T". The sign @ dove act mean mulipifation, fie sirsly gal that ch dret product of two mpremataions bas beet {ormed inthe manne given above ‘That theg functions do indeed form a hai for «representation ofthe point group ean be veied by considering the effec of tha tranfor {nation opirtrs Oy out = o.o. = 3rumrumns oan _— Dem = unum, 7 ou, -E0e 1H», a“ ‘whose, by ang etionary andr, the sum over p and g Heomes sam over», The myn, product-fanction 9, are thus trauloined ino neat ‘combinations of one another by the tranformation opertors Oy of the group; thay theseore form s basin for the f=" TST") mene Aineaonal ropresntation of the pint group. ‘The matrix 2°0(R) hat corresponds to the aymmetty operation R ‘aquatic of oder nym, ae ty lteter tho (om) pbs ‘rudvets of each of tho nf elamenta of DUR) with each of th nt ‘ements of O'R), The matrix DR) x called the dizet product of TAR) and PR): Drop) — DeRyod"R, as ‘The diect product of two matron la quite diferent from the ornaey ‘matrix product. Fist, lt an consider how the indie of te various toatrx elements aro related. By computing gta (23) and (3) wobare itn al Bhi = 0. once the aubucip rin DZ3"U) la determined by th wbacrpte and 4. while «in detenmined by p and The distonary order cnenion eprmsontaons and Onto Mechanics 187 ‘then gives the following table ‘ i iH 2 ? pend ‘Thema table hold trae with jj, and replaced by pg, and ereapec "Sooo example, consider the direct product of 252 matrix A and ‘add matic B, then ogn (8°33) given y [Pn Bn Bal Jefe me aa Tau Ba Bl Abn AB AaB Be AuBu AuBe A |Ante Anke ANB AaB, AaB JAnBin AnBu AnBe AaB Anan J4uBa AB AnBu AnBn AnPn JAuBo, AnBen AnD AnBn Aube ‘which cnn be paritoned into four euraetroce LAB | Ais sa in vorydifernt from ordinary matrix maltipiation "The charutere ofthe direct product representation will be ren Sore oZ ZumDum Pm) a9)158 prannatios end Gunton Macuser (the eat way of confirming he wbecrpting weed here to lok at (63.6. "Wo can of course, ake the dizeet product of more thaa two repre: entations for example ersery wan ‘il, by extension, lao be sepretntation of the point group. We Spy aly the et pct rae wie: The rato he rR) = LRA. In general, the dire product representations are reducible and sing the formulas of § 74 we have, fare ied epreentasone ror = Zar (e39) (b= numberof clases = numberof ieedacibe eprestation) Pen eo Eee me — ot EUR. wa.) ‘This technique of decomposing a direct product representation wll be ‘of great un a th next section, ‘The reader ie cautioned hes the trea direct product Ine & eeond smeasing in group theory” I the group 9 bus Uw semente fue {nd the group 2 ua the elements By hy. ead If gy = ha fot {Ss and‘ then the group whine elomente ae bru anid wo be the direct product of group 9 and 2,05. Su = 2.0%, ra = #Stet We have alrondy some across tie ivation in § 78, 4, vai ne Th thn tone deve cern le which il determine wheter ar nat nog ove geen sinner maar varcfenetoas ia, tm sch rule an ade apc eeton rae one th int Jeenrionyan ar uh), a1) oh Mroartlon and Qateen Mechaniee —168 srhereyf() andy) ate elsctronic or nucle wavefunctions which ‘belong Yo energy ives, and, meapactively nad frm bs for the ferodactble ropremntaions [* aad I". ls the tual electron oF nbdlearcoafiguation and 2*(X) ina give famtion of helenging tot foneion apace which wo wil amame geteratey the T* imedectbio epromtation, The intgration i eariod oat overall ofthe electron ‘emuclent coordinates Tein epparent thatthe integrand, vOoP Ey, 4 one of the buss functions Sor the direct product representation Evoror™. (Note that y(X)" belongs to Pvt If wo arty out the reduction ofthis representation ror then the orginal baa functions, ¥(X)* 2") 97), can be expe 'm terms ofthe asin fuotions which generac the iedusilo repre sentations Tete OOP = ar ted 4) 16 90 aply tothe intagrand the projection opersior P* (ove $7-8) hese P= Eytnro, atte oun ad i happens that PAP PDE) ~0 then 1* docs not appear in eqn (6-41) and f* dos not appeae in eqn (42). 1F Parner” does not contain 1, the tovlly syametse ‘epromntation (for which 4(R) ~1 for al Rand P= $0,), we vil have * 9 FUP) = FOAM. (643) Bat th Oy are ouch we $5.7 that for any fanton GLX) Jou ar =f 0,0. ae = f oy0tx) ar, AHerefoe eumming oer alt R, 0 fo ar = fF 0,a¢x) ar ‘here is the order of the group, and contguently J venrmenyen ar =o | Boston rony a ae160 pranntations td Ont Mashaice “ence from ogn (64.3) we have th important rev that the integral SpA Py dr wl be ec if Pree ot eppeatin Pee PeT? (thi ise suicent bat not neasnary condition} "This tame condition may be exprewod in an ternative way. If 1£(G) se the character for any sataent in the ith an inthe Tie {edusble representation, then PHC) = LEC) (ote that °4(G) = conjugtte complex of 27(C) ~ "(Gand the eee ee sd raallng ean (73.6) andthe fat Ut T° ad 1 are iret Pepmemntations, ohare ga 4, 49 Hine 1% appears once in TOP" if p= and not at all if wv ‘Now consider the dwt product representation P1017 Iria the ‘adaction of POT” the representation [dos not occur, dhe by eg (648),0, = Oand Peer ol” doce tot contain Fv and [vcore ae la zero, So that reduction of POE and chesking whither it contann Tor ot ia all thats roquire to ace if th tora vans, Ali PCH) is replaced by am operator Hi which belonge tothe totaly symmetielreduibe eproenttion T(R) 1, al If thea fverrnyan ar nla I" = 1%, jo, unlass the two wavefunetions belong to the same Inreducbl epreentation, srpetix EL. Prot of gn (82.12) 0 (8.2.18) ‘The proof of thom equations flor that gives by Schonland, ‘To prove can (213), mar fen agi pin th cordial y, agus te operon Re ove tah wher bh ° 45) sodomy, fauna ann ear st ee tan 1 se cares te tay pepe ma Bal omnes Epamogma, 288 a Onsen = fled tite tra sae fen thn ep pn, he On ae Yann) Teneo. ania ‘Te igh hn sf gion oY ee = eate sn re ten otto ya Bete, BB OF 5 (asin K-REREAS remain, i Boum MoS Dum aden SF -$ S pumnume (2) sot ming the ston et th th ao EE Sonmoam2.() ie (weoegn(as.29) a See) aor. Ate pn tel © One a oq wet Pousti) POs a142 areentains nd une Macher kewie WYosa) = Deny ef and age (A813) bomen LOW" Phe #) = VUORN 2001 sad ice, 2 oeurUroughoat thin equatic, we eoaade that 0,04 = Vg asia "Teking an eqnton ike og (A814) for each elotron and multiplying by ibe and adding me atta sgn (3) ‘To rove egy (62.1), tm spore thet R, whan tapi to he oseattamewont chug any general clear onus fren Ty, {S'S thaw the bas Saco’ as tauren $4) So S250 eho, in eras ofesotnnucratertbea tssveaeees eo outs rier odaplacment fom the aquirium potion of ucla gas bn ‘atina the 9 ogons (oe for soc maw i eg (A 819) fr Ge ‘aerators together to eben 4 38-dineainal mas} knight cage othe dervauon ofoqe (A814) hen eet O42 Fund = VI0e! End Boca fn attr of Rand gmt be yal Metal nd hr fans casts) Onde 82a) = EL VOaf End sn 09 29S ation [any general near sonar Yq, bones eye Wont eae) Voli aus nV te) ~ Vana) = Vand Kin) nF se = Foe OY f Eas) ~ OV arf Sand) fo OuS Kane) ic ean (216. eat wee prov na 8.2.10. Yi fnstion ofthe lative pions ‘ofthe Scrone and boll tat Is Y= Yolngu) here Xyerih Oe araertains nd aan Mechanicr 163 ce tthe spate nucle conguaton wed to da the molele's predecessors selSeetanged tad 20 ca Yalan Kaa) Vole Xe 1 we now apply R- to the neha lone then, since this only interchange {ike nua sly denon Innes the nushar Eeteework scaly tor ‘haope Yat rennet sane Vol n Kae = Velie So that for the frat nedear conigeration with deinen the mole ‘named By Ry Xa Xi [fcven ¥ anchnged he at ofthe post af eqn (02.4) ii mae $8 14. To cht oma pemaion Sth Bilotng in pont Go PROP, Pa gTHy PAGTH TEGT fr ty ©) Pert. Org PHOT for Ig, (0) Pe@P, mre, THOT fr br 1.2 To what ida eprntation mt y bling he ner Jrcoricne ine ist nena in he filoring eat ven nnn ie bay Pon TO Oak el eronte O20 Lane eon,1x this chapter wo apply the reales ofthe previous chapters to the ‘problem of molecular vibrationn. Dafore doing ny however, it in ‘eoumaryhavesome knowindgeof the quantam-mechanica equations ‘which govern Uho wey in which moeaul vibrates, Wo Sind thatthe AGlation of them equations le greatly simplified by changing the ‘oorlinates of tho nucle! from Cartan coordinates to « Sew tyPe, ‘Sted in speci! way, called the normal ordinates, shange bs ‘bo more myetaioue than changing, sy, fom Cartesian ordinator to pol coordinates when solving the Schrager equation forthe Inydrogen atom; the bale principe a tho sane, namely the tnathe- matics Is made ease. So we oart thin chaptar with « dncason of ermal coordinate ‘We then disover an extremely Important fact; each normal co: ordinate belong to one of the Sreducble representations of the point {oop ofthe molecule concerned and isa part ofa basin which can be ned to produce that roprcantation. Beste of ti elatonahp with the normal soordinatn, dhe rbralonal wavefunctions aarocited wit ‘he findanental eiratonal eaerpy levels alg Behave In the wate ‘way. We are therefore abo to claify both the normal coodinater (Sod fundamental vibrational wavefunctions acwering to tie ay ‘etry specie and to predict from the charcter abl the dagenerciee tind symmetry typen which can in pints xi "Furthermors, knowledge of te imedacblesepreantations to which the vibrational wavefunctions tong coupled. with the. vatihing Integral rl al en good dal about th int red ad Rataaaapeten ofthe molecule wader onsideraion, 12, mama cori Ewe consider a molecule with mace, then the diplacemesta of the nucle from thir equiv postions in Cartesian coordinates fan bovwriten ae gigi get, ef” ‘and the correeponding vlotin aa EPPA whee ae aan, Molecser Virion 165 (Or we can ate the n-clled ma weighted displacement ordinate Bal (oan swith vost Page” a ant a? ~ ake ‘and, in the mate ofthe sh nucleus. Ia asta fast will be more ‘convenlnt to le the eabecrpt on the qe and g' tan over ll the ‘sordiatas and vlocitie, L.from 110 3N, eo ttt we have fide in place of oqo (2.1) and (02.2). Tn clamian terms If wo no the mam-wsighted Cartan displace ‘ment coordinates, the kinetic enorgy ofthe moving ie! at 1S Soe oon (thea term aro ofthe fails jm type) andthe potential enray {lative toa valu when the mole uci thei aif postions, nV, whlch canbe expanded ina Taylor tories EQ hE (Se )emre wan where the absorp O dant thatthe dvivative la evaluated when the Hudlel ae ia their equiibriom postions, Rinse, by datition, Via ‘nina forthe eqlieiam configuration, we know that a Ho beng a o29) ‘nd if wo repo the second derivatives (which ar ole the harmon force contants and oro Iatesle properties of the Mlacule, wader omarion) by ayo (2h) ire "Gia je nance snd tap the expansion after th quadrtiterme (the armone cecal ‘ppravimatin), we bare vid 3 aaat (2m TEES pemtahooge tatamrtin a geen rte osalee eee We to AQ)E-0 cone wan a Fo ME. 4, (0-2.9 ie [Now lit obaos a set of IN cooficente Ci, Cyan Cay such ‘hat 'shen each ofthe eqae (028) i multiplied by the appropriate ©, (apd the BN equations are edded, wo obtain sao, wary where io on E ae, (ona (ie. Q ia & Linear combination of the masweighted diplesement ‘oordiatee) and 4 fs 0 constant. Thre wil be, In fat, 20 waye of ‘making the choice of the 31 coticentn. Wo canoe the reanon for thi ‘by looking atthe oquattion which mest exit betwen equ (02.0) and (82:10), that i wo mt has Seka dt-a Gm) So$.ma-sZow 12.00 3N, (o-219) From eqn (#213) west gy, — een Ze, ingens janes ao Motte Viton 187 or tia wt of 3 simultaneous equation to have non-tivialslatons for the Cy the following equation must hold true (wn Appendit Aen): ee a) = 0 (on) ‘whore Bethe mats formed from the elements By and isthe unit ‘Bates. There wil be 17 roota vals of 3) of og (8218) which when found, can be wad in tum to alve eqns (0-214) for the C, (oa ad ional equation, « normalization equation, $ Cf = 1 is regsired to determine al of the BY C's) Siac there are 3 vals, there ao 38° seta of C, which wil prodeceogn (02.10) For convenience, we will dd ‘ rabeript to 2 and @ to datinguish the diferent solutions and aa ‘sional mabecript to the O's to show with which f value they are teeodatad, 1sden Game Cent = Hcen ioe ae outt gs ee Seed as ee "The Qe Qn Quy Are called normal coordinates and what we Inne done i fo tanaform tho ordinates to anotor set Q uch at ‘qn (0210) im trv Wo can form the matrix © by ting the scl {or each 1 aloe ae clare: Jon Sa Chan Fan ae on JCurs Cav Saal 0d since in symmetric tla matrix wil be orthogonal (me Append Rese, ‘Aa ella matting 2. +28, =0 aw oat)1 ar thes tora mi a wasn an = v na Bact (29) (hone equations ae proved in Appendix A... "The solutions of the equations of mation (eqn (0-218) are aay found to be: Oe = Apcos htt) 2 a ony) On Eee tana tin ss. nga vv = Send, contiterey sd i al the normal cordial are nro ens on, sy Qy (hat Bre escep fort = 8) then 1) = Geb 0 (8) eam sod cach mana woightod Cartaiandiplacoment coordinate ie varying ‘Sinuoidally with time with w fequency of ry where my — Jb Sach ‘totion is elle & normal mode and thice ae larly 2 uch odes, ‘sh one anoriatod with one of the 84 normal soordinatan ‘Som nuclear daplucnments wil be rach thatthe bond length and ogi the molecule aro unchanged from thir equilibrium valsce and is consequently unchanged; ouch will be the cass fr tration and rotation of the molcale at « whole. For non tinea moloel,« ig ‘movement ofthe molecle as = whole may be oxpreod as «combine ton of trnaltios along. and of rotations about, three chosen sxe ‘To. doveibe any general tranalation-rotaton movement” we wil necenmriy rogite wr coordinator and therefor at lat six normal Coordinates; hence Vo zero for at lent sx ofthe Q, having non tro ‘ale: Since Fe meusured relative to the minimum pototal energy (the vatas for the equilibrium munlaar famework) V 3 0 and since rat Sre Masterton 108 nave 4, > 0 (Qi alway positive). Now the only way in which 453 20% canbe sero fora oats of the Q, foo, ‘must be exactly abt , which aro seo teoauea if there were more one ‘would be able to carry ost nortsal tnode which io not eccmary ‘ombinstion of transitions and rotation and all have Y=, thie stout be done teat ithe bod ent the ago chenge the We therefore anoint, Oy Quy By dy Baal pots) sith wbralons aad Quy. Quran Gan aad apos = Aagna = Ba with trasltions and rotations and write va'S ua ors mar che a ny onde atin nd batten nner ra E at ‘The point of changing ffom Cartedaa diaplacement coordinates to ‘orm cordinetn in thet i brings about greet simplieation ofthe “ibrational equation, Furthermore, we wil sea that the normal oor Alinaton provide «Bais for representation ofthe point group to which ‘molocatebaonge. 193, eins een ‘The nuclear equation (eqn (82:3) written out i fli (ae) Pa a dar, Hd = Benda) (083) here the aymbos have been defined in § 62.1 pub to aproxi- "Date Fe 80 tho product of three fancions one a fancion af the fcordnsiee deeesbing traralation y", another a function of the oordinaten devcribing rotation 9" and the third» fanetion of the ‘ermal coordinates dewribing vibration y™, that Pane = ve, qn (0.21) can then bo separated into thee sigenvalee equations for ‘the thes typee of motion, The three eigeneaie will be: (rane latina eaargy', W™ rotational energy) sid "> (erations energy)170 AetctrVtretone tds wal mentrneey en by vores hrs Wt tae nrg oth mt ohn na ned pao eer ctelegl paper paterctt Sa eae ree ah me sulin sgn fbr peruano ts we ral Sera ping teas ta en Eso peal ape er oceans cesta ayaa psa Srnec ee [iicoepialbgee tetera “SB dnd re 1B) wt dand =o je sd i we replace WP by 0 sum of term we Sy, 20d y™(Gy- Quy-a) BY a product of functions, each of which in Sanction ofa single vibrational normal coordinate wee dana ha avo. (023) ‘ga (03.3) in the same an the well known one-dimensional harmonic ‘vclator equation and hee at oltions 4) = Keep ie DH. (10) os a = (act — 1, fa normalising constant and in coven och that Frteaa,—1, cosy den aa 8g ft, * m= 0.1, 2, (ibeational quantom number), Hi) = Hermite orthogonal polypomial, eg, Hs) = 1, Hie) a2, Hie) 40-2, Hale) = teh—t2e ta ‘he fundamental frequencies», (6 = 1,2. —6) aro related to 2, fd since i are the rots of det(B— 38) = 0, x, re rated to the ‘Bate Band to Ue molecu force contante Bene the vibrational soergy level for « non-linear polyatomic moleule ih the harmonic Usllator epprozimation atv given by we See os nd the coreapondig vibrational waveunotons are given by = earns Her (—F Ewe) Teale) (3.7) ‘od both Wand 9 ary arated by th value of he 207 ‘bratonal quanta mami mm un ‘We so fom eg (03.7) that the lowest energy state, the ground ole, carn hed n= mvs Mates Onn the energy a thee we Se, osm WF esate he sr tk nn hn gd ae aren we = teap (Ee) oan ‘where le pormatcation constant ‘Tho vibrational ergy lovels wore all the quaatam ouster are taro exwept for ono which in unity ae called the fumdomental lees‘Therefore the froqueney of the radiation sbworbed or emitted fm a ‘tranition between the ground state and 1 fundamental Iva be (WER Wyph = ry then pth fandamaental frequency. The. or. ‘ponding wavefunction wil be WE ven occ VII) ¥M, (03.10) ‘The infrared and Raman spectra of molecules are dominated by ‘ranstions between the ground state and the fundamental level but, {m preci, che tumber of fandameatal fequene oberved dows ot each 31" ~ ance () some of tho A, are ential loading to dogenerate ‘ndameatal love) and (0) selection rule forbid certain tranntions ‘Both (e) and (bar doermined by the eymmetry of the melecala. 4, The (oe) repconation ‘Tho anes weighted daplacementa of th nucle! of « moleela from their equiftcum portions gy an bo aed to genorate ropreattion ‘of the pot group to whlch the meleeale belongs. It under the apie ‘metry operation R, the made weighted mucear daplaomente become om Gi ine Sor ee sod the matress D®(R) wil orm aropreentation I¥of the point group. ‘Thin i junta generalization of what we dd fora singla point in § 5. In some books the notation DR) and T™ ie ted for thin repre: sentation, ‘Ateratiely one can et up mse weighted aso vectors with their crigion at the equilriam nuclear positions, and transform there ‘osloce with the aymtchey epertion R, then Be Ge tae (if we have thre baee rectors foreach of the 1 nucli) wil become oi in soa . rs (eee § 6-4) and me wil obtain rpmwaentation T° dentoal to the one Defoe. The matin D®(R) wil be unitary and T¥ wil be a unitary roprenmtation (uv tho matrix elements are ral, the DAR) wil ‘etal fac, be orehogonal) Meiers 7 We can change the bala ofthe above representation by evitehing to normal coordinates for normal sordionto vector) and beait representation T" which equivalent to I (eee 3), Tho change ot ‘a dined by (oe eqn (22.20) Eta, f= 12.030 = Eerde $= 1,2,..38 ‘od th matsioen DU ofthe representation 1%, which e equivalent to rare found fom % -Eonme, 4s) 0, =05 -S0x1m0, oss) ‘Since the representations are equivalent, the D'(R) matrices can be found toes the D*(R) matrio By » sniartyteenformation and in Appendix A.-2 we show thatthe tants which dove the tranaforming in the matrix O (formed from the oecients ,) 20 thet DH) CDNB all R, (45) ‘Sac th Can DU) ate orga min > ne Apne Aete). “Aa an example ot ux comer thro mt of baa vectors seociated vith thee intial nucle! whic, in their eqn Powis, are 1k the cores of an equilateral triage (wich atom belong tothe 2a, ae esp Pig 49. For the emicy open me fom eg (43 Seton e ite teste al avata| ete e Mitt sile lavas alG| © 0 0 0 9 ©» 6 4 Pati est ott tiie tert sHttiteitts mey=|-vaz 20 0 826 0 oo Cotte iieliie Mie iivelita| © 0 0-2 yyz0 0 0 0 0 oO -vyp 20 0 0 0 o 06 6 6 1 0 0 ©176 Malai Vinton {If we make some reasonable ever ptions about the force constanta By for ties nicl! in wh framework and save the equations det —a8) = 0, Ze-rrvoano, AIO Y 1.2.03 = (etaetviete VERVE Os =f) Hn Vimar Ve— OVE Of (tt Vineet VENIYE emf = Cretan t200/2V8 =o) (2 Ba tanntys =o) Ant vine Ve aleva Oe 0) = (atatadiv y= 9) 6 = 04. e—anlV8 w=o = anv? =o ‘where the numeral valu off, df depend on the parteuaechole ‘SF Toree constant, and Where 4 to 2, sormspond to translations and on 2 0 o-2 0 0 0 Cit oiie eto ti olieltavaliiial , [i cvs 1 0-2 vaio oo wailve 1 -ve2 0 -1 0 0 8 SO SHitettte ints ee | Lea tte es eto aan ye Hate tHe ani atta Sitio Mirae Mo um all all myelin Molec Virations 178 sd since Ce orthogonal (en Appendix At3(6)) 1 = 0, We ean ‘ow eraluata D(C) fom DMG) = CDHO}E = CACO cient on ettotot eit Jo iz -vy2 00 0 8 oo Svea esis itino Heo ntertiitAt Biotest vedio teit enti sfe 0 0 -vap = 00 0 Scents Hien e Hat raTthta Ho on L nett etiotl ys a ee tet St er anzas as oe) ln apparent that D%(G) in biodk frm and singe the same block {form appears for all Ue other symmetry operations of the osnt group, the T¥ representation hae buen reduced By thn change to the octal ‘coordinate buss That nach reduction wil asaya eno, i= plat taken up Inthe next section, Necdlea to any [® aad Ihave ideatcl sharnctrs Lo. 8) — 7B), for al “Tho rnder might note that once the matrix © hasbeen determined ‘8 pombe, with the aid of eqn (8.2.21 ogi a pltar’ of «normal mode. This ie done by depicting the aplacmontof sach nucle, st som instant in th course ofthe normal ribeation, by an Aro whos length iv proportional to the dapcement. Ia Fig. 841 pctaree are ven forthe fit tree normal oda ofthe previou exemple #5, meraacon ot “The previous example was not an excoption: it generally ive that 1 oan be reduced by change of cooninntes (or Seas vacton) from AAA eft 7 1a. 41. Te al nh a ln176 aaa Miron 110 (or q 0 0), As has bon mentioned before, the ease 1 valee fay oowur more than once inthe sluton of oan (0-218) in fake Xow for sure that 2 wil occur six time) lt on eonaider tat there are AF distinct A valuoe dy fy and’ iy and group together those sermal coordinate which are tanoited withthe me falas ‘by eubwcipting them inthe following way” any Be aay Ge Qa Bag? Ae a Qa ings ar wher ni the number of normal coordinate aociated with 2 ofthe ‘umber of times i occur inthe shaton of eq (02.18). "We an then replace oga (03.18) by vt E 40h on) sede 043) by ae Sn EF Prost RRan ona 0d we can prove that fw Prow(R) = 0 (oral By (ss) "Tho implication of this let equation is that the DUR) are in block form with each n,n, blodk coreaponding to, ivotea 4 vluee, fa ‘ch Boek correrponds toa at of dogenerateormalsodinaten Wo can prove equ (0-6) oe folloms Lat Q stand for sok of ermal sordinates which reflect the daplacementa of the nucle! from hair ‘sulibrium postous in some general alear configuration ry aod fiiry Tet Q” dain them displacements afer they have Bee rane {erred by H to othr (but ientcal) auc. "Than the relative petions of the such ae unchanged by R sod since ¥ in w fenctionwelely of "hee lative postions (wn the footnote to oga (0.2.7), we mart have 7) = Me oA. Now 701-18 Bact EF AES ransim eal SE Peanuts} HAE EE 3 FS s.0hesntienol Reader . 10) ~1¥ Baca smi ‘Since D°(R) i orthogonal ‘4 maliplying eqn (05.4) By Dina (R) and suming over «and b, se obnan FF veeeuttatas aE EADient de « A Diol B) = AD So that fu» and consequently 4 xy then PhoaslR) = 0 sand we have shown the trath of ag (2). ‘The Dm) m1 mH cpume xR) =| 1 1) DH ‘ith db same block form forall R, where DCR) ie n> matic Sete with 2 whe eras he eprenatin (] fectangular arvay with all the lomenta sor, Te tures out (0 th text nection) that Uhe D'(R) can be amare tobe edule repre ‘otatons for the pint group eonernd17 Meter Vets ‘ur previous example of thre nl at the corer of an equator triangle (ther equim portion) elonge to the Se paint groop ‘bd ge (046) can now be written a Dre) = Pc oO m Mm wm oe Oo OM M oO O Pe mM w@ jo @ @ He o@ w oo 7 @ @ HG ow Po @ m@ @ © Drh ‘Ther are similar equations forthe ater opersions ofthe point oop} ‘Therlore, forme base for the P= representation and ina wiratonal ‘normal coordinate, Qy and Q, together form a bai forthe T™ rope entation and they are alco sibratonal normal coordinten, the Feet ‘orrepond to = 0 and are tranuational ot Platina otal to ‘ordinates, Gy and Qy belong to T™, Qy to TA, Gy to TF Gore 15, he casino sonal eerdnsen ‘We are now i the position of being able to determine the eedscibe repreentations to mich the diferent norial ‘soordioaer belong. rom ths knowledge willbe pouibato Sind out which of the funda ‘mental frequencies av intt-red or Ratan active, The redaction of > (Gbich is eptvalnt to 1) gree PEM -Por.eMtemaren where IS soereponds to the traaiatonsl and rotations! normal ‘oordinates ({ = 0) and I” to the vibrational normal eoordinates Of ‘our, in the shove sequente some of the 's may be the axme 968 {ignore the pomible occurense of acidental degenerie where the 's ot because of aymmetey but becatan » fortitous at of {Soest Maas Vieaoms 178 force constants B, exists, On the othor hand TS wil be reduce. rom the eharetary xR), 2©™(R) we enn Sod 2°(R) by ting 2R) — 2B) —20R) snd from the standard decompoition formula (oq (7-42)) we can, ‘hen fad the oumber of aiatnee fndameata lovels ad ete a igsneraces. The ireducible opreentation I" which in generated by aw (= 1, 2m) incall tho opmmatry epecinof the coordinate) Gio 6 — 1,2, m) and ie detainee the Wbretional election ral “Ther are simple formulas for finding th chareter of T% which cut am = Eaten a nena to the diagonal of DAR) and, referring to § 62, for thee there 2 ‘entsibation per mucous of R|E oH 6 sm + HRY [ 3 1 G8ee0 Tee Since E ~ Gian), © = Site) and f= Sia), wo can abbreviate things ‘oven farther and pet A) ~ mexiR) oan HR) = 1420089 for Rm C1) HR) = —1420009 for B= S19) ber of unmoved nucle 18 i alo quite straightforward to daterming the character of IM, ‘For s\now linear melacelo there are three tranletionl normal 6: ‘ordinate and. threo rotational sormal eordicates end we, write Ti = Mer, The traiatonal motion componde fo « dielaceent ‘of the molecule in me arbitrary direction nnd tena be depicted By 8 ‘ingle vector showing the diplacement ofthe centre of aan Let Cie ian ectemtany (9, and + ao Cartesian coordinates). Wo have shown befor that symmetry operation wil ranform tha vector to etyetie, hore 2 and are certain liner combinations of, and x Thea ‘the three tanalational coordinates will generate excctiy the one "eprsentation that in gaerated by postion vectors in pyielspace hareland we conciude Ubt tho et of cordinats 2 y-andsfrme a bai for {re-limensonal representation of the poi. group wo eal thi foprcentation Fat) wil be etal tothe xR) given blow am (0-01), Ths ieedaeblo rpreeentation() to whieh =, y, and = ‘long areca given inthe sharacertablenf But note Yat" 9 Ie character tabla haw diferent meaning from ‘a, 9s the abwenee tof parenhnees indicate that forma « bana for w one-dimensional {Ereducible opromtation nd y forme a ba for the sun irate pretation nr, while the prvence of parothae indicates that = {Indy together form» basin for two-dimenaionl treble Fopre We must alo find the apmietry wpcon ofthe rotation and {olow the telment give by Lavoe Ap abla Nii tation {ho motels can be reslved ito rettions by vero ange tout te {heer tmnaationl ae my. sod 2, We cau opracat the rtan ‘a hs b's i abr ping ng th on (Gren by fhe raion the apa whe the gee the gh is cul inthe dition of tation. The sfc of ty ymmatry Cperton oe the nucone doplscuent vets os eatos dodanie ‘fet on Mh the Cy ston aout the! axa sends te alec Stunt vectra for tation shot theses ita tae bogative, heey evening the Section of thir ot; bones Rhone diction x {ined itive to the dreton f rotation rorred in dation Stetcaton in eye ple og hse ett onthe Saplsement vectra Tocroteion out tle 2; hens i sochanged by this met Sertin, Thor the ft of gon Ree fo eek ov a rest ‘Untng ong th 3 asi nf epresatng tunis! maton the Etc ntctor chnaged tits opie by we Pig 9-03). Veto Motte Virion 18 like Ry are called ial vetomy oF pecude-vecors The symmetry ‘operations tamara each f ten axial vectors refecenting elect rotation about the ay, and + tae into liner tombinetone of one ‘nother thereby generating th repreetaton I, which soreponde tothe moleulr rotational moder "Tho character of I" are related to howe of, Consider Seat the sifct on, my Ry. of C{6) rotation about sone ain ot necemarly {the x axin. This otation will move the rotation diplnccnent veto in such 6 mnaaer oe to sranafort Ry into ‘eetor obtained by applying C{P) direcy to Ry ‘Thus for peer tations, the matte denebing how Ry Ry, ad Ry transfor ae ‘actly thove mations that desrbe Bow orilnary ponton vectors ‘long thes, and» axes tranfortn; the matrix in the reeset Tr coreapring to any C(O) in therefore the sare a the matrix nT that conreponds to O(0) and the characters for proper rotations ate the same for Tan fr I ‘Now consider the eect on R, of S(6) operation, We have 50) = 61) ‘The C(6) part has the same efect on BR, at on taatatonal vector slong tho = xia However the effect of urlestion on Rs oppo {ota effect oma traniational vector slong the» xia Phoe iw matices Aesribing the afc of 50) onthe rotation vector are the regulates of ‘he matron danrbing th efct of 0) om th teansatonal vectors ‘The charactor of any (0) for T athe ogative fie dharecter fm F Summaraing, we ba r1c1e) = 200) #1810) = —2450) UR) = 2042 008 8) R= CD) 2%) =o Ra 5@, {ewe return to our equlaterl tangle example and apply the above rules we obtain the nusmber in Table 861. Using this tale ln oo jimoton with the py chareter table (Tabio -72) andthe decom poston rae: amet ErmeR — + SoCo Rerrene rover soa Papier,17, Fart eampla of wormal carknte stoton In thinecton threo more examples normal oordinte claifcation sce given, Wo conser (1) 140, (2) COF and (8) Cy (2) Th character tae for Ue point group of 10 ‘ye i given in ‘Table 7.1 and baw it we show tho characters forthe TY represen” {ation (found from aqn (-6.)). Prom thee characters we obtain Paso reat osrm ‘A in orval practice, the representations for T¥ and Fare alin given {nthe character table and we dredy obtain Parerkerk nea Pare rhort, Hane, by nobrastng thee from I* we hare Peart ort So that there ar hres datint (having diferent so #8) non degeoee- is vibrational normed modes with symmetry spesia T™" (Oro) and 1 (on. (2) The charactor table for Uh punt group of CO} (9q) i given in ‘eb 07. and below 1 we show tho charwsre for the reprecet ‘tion. Prom thes saracers we obtain aD @ PH @aPF oar oir sad, by inpoction of the tab Depron oa Poror, Hence Papi g arr 9 rie sd there ae to distinot nonlegenerat vibrations! modes of speci TT and T° aed to dutnse doubly degenerate madar rith the ate symmetry species FF {@) Tho character table fr the point group of CH, (4) Se given ia ‘Table 073 and alow ft we show the characters forthe TS repre sentation, From thee charters mo obtain PeMeror oat 0d, by iapostion ofthe table, Tart Tame 9.7.3 Character tbl for Fy104 sae ito and rer, Tense re rhert oat frsona normal coordina ot mode) cabo dani si henner day agents se Ser ee ey dana a vg to andthe Tae git cote eume roprnetion FP but with leet Ieee trom he previous oo 14, terme cordate ine molcen “Linear mcleclon belong to the Tay foi group if they are un ymimetria and tothe 3x polnt group i they are aymmetical, Once YELP hey aro spel case and we wil en atte tbe rata There cea Ay sds of normal coordinate fr linear molecule: longitudinal, TSIEN Ge soar hove wedergone longiodinal diaphnooments along Aiaasitiar ara end treaevere, where the nll have Doe apace perpendicularly to the motos axa vingiseal somal eoorinains belonging tothe aymmeteyspesen TRORSGE Sp ant they er he lngitudinal pe; aod V2 pry Gerona ermal coorinuten (doubly degenerate), each pair OSIRIS to tae th aymmcty epecien and they are of tho tranevere ope i Pe aymmeticl near molecules, if there la an even number of ee ea sibrational normal coordinates belonging 89 2 ‘Piatt tmging to tne aze of the longitdinal pe) and has se tat Mate belonging to H, and 2-1 pair belonging 10 Te Maen tre tronavern type) chore i an odd number of noc, (RES ys vibrational normal coordinate belonging to 3 and UTI Seioaging to Et (le are of He longtadial type) and aN pairs bobgig tI, and (—1)/2 pair belonging 4 1, (thes sr of tho ener 172) 1, chain th ein tae “suuniing the viratina energy rls mean dog owt 0 which setae esatin oe nnn Fi ste n ia shy couned wks «ren ove one, ey ie trac god tae Thm orepnding seevettntion em eqn (23.9) Wate Seat Molener Viation —105 shih, writen inthe pla of § 85, becomes wwe tEn Eta oa) Under the symmetry operation he nora sordinateQp it rane formed to Yj aisha » Linear combination of Onan. Ong, ad Since thes eourdinetes frm «bana for the pth freducble Tepe " Gras = EF Dkat RQ hich i th dao vo’ of og (4.3) and wha 7) the “tite praing X's tho gi inedeae romana’ of he Flan gop to wth the sods aang ie DU tog Sal te inden! sine DPR, nts be orthogonal Gen = E26 Rn oon Xt wo eubwitte eqn (0-03) neg (8.1), wo WM) =H ern( Aan 5 FX orm vestmeonden) (oom har the @in yiMO) indicates thatthe wavefunction take he rao {the normal sardines bore the ayrutny operation Bien, Since ZUR) is orthogonal Eprumoem ~ 4 nde cn pec og (004) 87 0) = Neso(iS «EF oseuuden) =Ne(-iSs Eor)- wre oan Xe re das the ymmateytenaermtnn operat On te al my ty Ove™(@) = HO). we have fom ogn (00.5 Oita = wD oon ne,Cconmequestly yi* generate the ideal rpremotation I of the pin ound nay thn ate vena aefneton "The fundamental vibrational enorgy love at an energy hr, above ‘he ground state, Each orl at anointed withi¢ mcutan fandammental frmyemy 9, ad therefore curtain A val 2, nd each 3, hae soci sted with iim, normal coordinates Qjay (0 — 133-8, Coupled function ya which in proportionl to wi"Qyn (ove eqn (@-3.11)) Thea the fundamental loves have anm,flddegenercy: What the ary ‘wevefonctions having the mame orgy Tee write thon degenerate wavefunctions at VD = MYO any m= BeBe, whore 2 lea normalization constant, and aubtivoe eqn (0-98) and (0-85) we get wad) = Hera) $26 = S Dm 260) = vue) = $ret) wt ons Zvtinnt “Therefore the wavefunctions yf, (m = 1.2,-.m,) form a bain for the Irreduibe reprccatation 1%, he seme reprosntation to which the normal etordinatss Qyar Qqigp soodated with the fundamental reguenay ¥, belong. "This el in romendouly maf, tot only lade to nection rales {or vibrational spetrosopy Dut also, a was the cae with electronic ‘revefonctions (ne § 62) allows unto predict from inspection of tho ‘Sharactor table the degentracios and spmuetion which ar allowed for ‘the futdamentalvibatousl waveuncuone of any partner molecu 110 aed apc “incident radiation with frequency equal ooneof the fundarental ‘requis fla on » molecu, itty take 4 transition from the sound state to the appropriate fundamental level. These normal Srequncie uetally cco inthe Infcwned spectral region, The pro silty of ech a truaftion occuring, however, depends on the ration ‘hip betwen the molecule’ elect diate moment (a= funstion of ‘he nuclear coordinates) and the wovefentions ofthe ground state and ofthe fandameatal lew Consider a ast of mutually perpendioular ax ostomy y and ey) with tel origins at that point ‘Thich ttloved by all the aymmetry operations of the point group Un let un peter the postion of any mule to a st of axes (paral to ‘x andy) whows origin ist to equilibria poxton ofthe nudes ‘That the saver pale moment of the melecuo when the nue and ‘lectrone nro in pout deeesbed by some conBiguration X, le the on mite tmtXer tne mit = See ‘yr and y ie proportional to Elf viewnas)" er the integration iver th whol rng of he ala sort, Sroneueatys tant on Se vital rou ate he finda etn hs sree 3 Jrmnyedr =o je (2,95 an ll vos (1, 2, a 3) ho ecto Sed ay ei cme eprontton ash roel Srna Serbia aa there Dune, sad i an esily be shown that Ov = 3 Piha, ‘Therefore the p(X) form a bass for TS Thre wil bo a partonar ‘holne of ten yy and whith will mde T* to the irdeto ‘epremaations which i contains ad thin choice ie the sam ae tho ‘hoi of trenlaionl axon which redueee T= Therefore y belongs 10 ‘he snueivodocbe epenetation sa, q elonge to Uh ame ont a {and pn belong to the same one aa, ad thee cam be found by “Sonoulting the appropriate character table180 Malar Wiaton Since yi® belongs 10 and yf belongs to 1%, the conclasous of Sede atten tnlea 1 coincidan with the ieducble representation t0 whlch Tdonga. Wa san thrvfore obtain the sleton rule which governs the tranatonn from tho ground stato to the fundamental level», only {neared active I ita aymumetey specie [athe we ae on of the Iereduble represntatons contained nT “An alterativo bot not so general weston rule ti restricted to ‘he harmon olator approimaton) that Jy" my, dr tro If 244/202 (orauated forthe equllbium buclear configuration) i er, {eit there lao linear dependonoe ofthe dipole moment on the normal ‘online Q "This eelcton ral may bo Found by making «Taslor serie expansion ‘of mit) im tha normal coordinates Qh Qs Quy (re FeV Wo UE initial notation). mee SCBTas ton bmn 30 “where the suporeripe indicate cralnton atthe equiram configu sion. Ifthe vibrational wavefenetons aro writen 6# TH wi Qe srhere mi the ih wrational quate number, than the ground state ‘avefuntion we Twe.e9 ‘20 the wavefunctions for excited states in which only one vibrational ‘Guastumn number ie non-zero ae va [Fp cofatmscn J v6. Qu wk 0.40, = ba (he harmon onlator functions are orthonormal) we hare Since france = A(FE Jou. eor10.09 00} frst. 0a tn dat xf. 030320 raya 2 et (22 CE Jos. or 90.00 20} rs 02renratr 0 en “higher tar, (104) snd ifm #0 the fet two fora and the higher terme are aero and frimnnade = (227 frf0 02M@aratre dn (262) 0, tue probabiity of the trenton fom the tod sate occuring ioe, for the tention {i take place the dipale moment mort shange inary withthe normal ‘tordinate Qu Sines ya(0/OnJ0q i proportional to ya(l,q) and the funetons ‘lt: Qo) ae othogooal, ii our that Jvn(.QaOaranar Qn) da =0 ‘Sowed Tome grove. Ths ey tr oly win ie “Sprosimatinn we have hn making in ray, tenons 0 ‘tervoon ove ne 1) do take pas oe 9) "erinsm acts foe he pnd toed wae for vtich more than oe vaional stant nah oor ae Ferien og ifm, 7 Oa my 2 Onto wate, then a Soothe itegal Jou. days sand fs, 9 re 00 84 vl appear in each term of on (910.1) and henae the probability of The tation ser. Again this ony arely tae within the ap prosinations we have been making and tenzltons to wo-aled oom bination lve do in actual prectio our (on § 013). 211, Raman specs ‘When an incident beam of radiation of frequency » fala on & mote culo, nme radiation apatite and in thin eatored rediation me gets ‘te well an, roquendea yz, wher, in fendamental frequency. Ta {ale the aman effet ahd wins fundamental frequency spears {the Ramen spectrum i i aud to be Raman ativeAn incident radiation Sed with an lectiovetor indus « dipole moment Ain molecule, Th somponenta of Mate ees Ba BeBe Bes boul Banas inl pone 0d su so se 2 std ny dotne the polariabilty of tho molecu. ‘he iter are transformed by the syrametry operations in the ame ay soaks oh oh nin ann eed cosy Whee eBay are he eo ruinatee of point in puyueal space (ae Appendix 83). The ax Polaiaablty functions generate reducible representation which we {whieh af (or) 24 (or yx (or 2, 2 (Or oy) ty OF 2), ate (cr yo the necteanty combinations, blong ed therefore give the ‘Segompition of Por example, fr CY, (2-)2-+9" 4a" bongs to Pavan at yuand ty? fo T and ay, 2, and ye to Fy, hence Bo rhertort Goan mechanics al om that che probability that Raman seattering involve the fundamental frequency y, depends on the fnteprle foemnae jana ‘nd therefore +, in only Raman stive if epincids with one of the [reducible Tepfwentaione contained in I emember that yf ‘elnge to Fi). This rele in eguivlont to saying that», only Raman salve ifthe polaciaablty changes daring the eth norinal vibration. "in » molecule with a centre of iverson, the Sredactle represen: tations nT" aro af wtype and thane se I ae of type and since T™ cannot coincide with both « w- and a gtypelreduible rpeeentation, ‘no fundamental requeney for this type of moloale oan be Bath if: (412, Thana and Reman pcr of and C10 In his tion owl determine the difornoes in the nfs rd and ‘Ending the number of aetvefandamentale and tir eymmetrie forthe ‘to mole {belong othe 7, point group (the aymmety lament areshown in Fig. 443) und the reduction of T™ was card out in $9.79) thermal th po ra Ih earh ‘arthermor, nape f the character abe shows that rere soa ram 0d hence pa TL Alto from the character table in Appondix I, we bave Partorer, So thas the non dgeneeate fundamental level whch belong to M gly te Ratan sie (fetid in bat not the ly degenerat fundagnental lel which belonge to wll alo ‘only be Raman active (Its contained in T= bot notin 1) and the Oro tsiply-degeneratefandamental loves whish belong to Twill be both infred and Raman active (1° f contained in both P* and), ‘CH,D belongs tothe Gy point group ui the C-D axia the yaa ‘Tho charster forthe T¥ rprearntation may bo found by ung eqn (04.1) and thy are feet eI seal ed rece Iisa mons ‘Thee charactors together with tote ofthe imeduciblereprecntations ‘ofthe point group tay be fed into eqn (7-43) andthe relution af > Sarvied ou, when ti a done we obtaia| Paurte roar ‘and since by inpootion ofthe chasacter table Partort me reper eee! raarieart Furthermore, Peart oar"st fandameatal lovee belonging to T* are alo both infrared and Raman active io for CHD the numberof fundamental freqescian which appear {in the infeed spectrum and the Raman spetcom are the seme, ‘whereas for Cy tian ot 2. Thin i rficiont information to de lnguish between thet molealen {C10 ia prnafbe to exelte two normal moon simsltancoely then & traction oan occur to what sealed combination lve. Sach love (Til be characterind hy a ct of vibrational quanto netnber hick {eal sero exept fortwo wih ar unity (vee (23.9) 0 wl le [San coergy of ivy) above tho ground ate Whar ry and > a0 ‘the relevant fondutental foquenson, The correspondiog vibrational trevafantion wll be ofthe forse VIMO SIERO snd as there are nn produstsof Qa and Quy the combination lov ln the harmon oltor approximation, wil have «degeneracy et to mone The nen, wavefunctions for « given combination level, taken together, wil fra ban forthe dret product roprecentation [YO T™ ‘Thin eprewantation wil In general, be tevcibla. There wall therfore ‘be combinations of the functions Ny~OQrf2ain which will form ‘aso for tho ieducblerepreentatign contained io T"@T™. In the Darmonicoeilator approximation thee combination reall egener™ ste; however, ifanbarmonke terme wich se 132.3 Ge Sraaleen ‘aro included in eqn (0-2-7), Un tia degenernay in tad and in place ‘of single combination lve ther wl ba group oflerla with nereee ppronimaely Me, +) grotar than that ofthe ground ste aad there ‘wl be one auch evel foreach imedusble representation contained in Tor (ooo $3) Hf any of the irl representations coined wth those found in Tor T* then « Bequeney approximately equal 77 wil occur in the infte-sed or Reman epevirun. Bloor thew {ramuitins are forbidden nthe barmoni oelatorapprotination they ‘il be wenkar than the fundamental once Motocar Virion 180 ‘An overtone love is characterized by a st of vibrational quantum ‘members mish are all eo excopt one which aa » value gretor that lity, ony. Ifthe qutstum number which enon or correponda ta {Fundamental fequoncyv,, then fom eqn (23.9) we wea that the over- {one level wile mry sve the ground rate Is sun be shown tat if the pth fundamental level ie now degenerate thea fr m even the ‘overtone level belongs tothe totally yimmeti rpresentation and for sm odd it Belongs tthe same representation aa the pth fundamental evel. If yn dogeerate, then the symmetry species ofthe overtone ie ‘ifjalt € determine and oncn agin ahrmoonie eect doatoy the Algenerscy predicted by the harmonioouclator approximation and ‘ow levels acy erated which belong to some dfnite symmetry spain ‘Though the probability of « tranition from the ground stato to an Drababity oan be quite high when anharmoni rma are taken it ‘fan active fendamental Ioral happens to lie clove to an overtone or combination lve withthe same symmetry specie, then anharmonie terms in th potential Y (ae eg (2.4) wl hove the eft of mixing the tw levels: Twa ne levels willbe produced howe wavefunctions ‘ons ofapprosimataly equal amount of tbe wavefunctions belonging {a the fundamental and the overtone or combination level. Touch ‘Greumstancs rather than having one strong (Eundamantal) and ene ‘weak (overtone or combination) transition there wl bo two teong ‘tanstions ying low together in energy. This phonomne i called Aopen AS Pot of gn (8.2.17 ne 21“pensation Sout = Aon EE iia hae a Oe 33 (¥8ounca)em srbeh proven ega (0210), A82, Potter Dm) —o*2%UH0 feng een Soc. (A022) (cieotogn abtiting og (A922) tvnino an (A.92.1 wn bare Souno.~¥ mum 00. Sea mre, = ¥ sod by equating the cote ofthe Oe 40S on Seaman -¥ mune, rumen Zeon Dimes etm pape 103) Zagl 208 = Seerr$ oan, ge) nama 29 = Eran Seater $name, Sean, oa = 3 Spams aie sim Station oy CA nt) = ¥ § Dal Df Ral. febeu te) = 32, eal how that eatstisin) = $ param “te it of pos iy en nm 9. Yost 1 sen epi ous‘Sehyrpe maa tral yah tts Spe CDSE atm en Dir ot gd re oo Sone ange by Eh oP ec ary oth on Fh flwing ain Molecular orbital theory 1 thie chapter we wil consider how to apnly « knowledge of rmctty and teraction tothe determination of electronic {funcons. We wll dow hy looking at «particular hind of spprosizate lectronio wavefunction for conjugated molecales. The Sebrodinger ‘sqntion forthe electrons of « molecule, our tating pointy i unt so ‘had to solve as the Schrodinger equation forthe nucle In the lator ‘ise we wer able to find approximate solutions by relating the tree poteatal nergy” J with sum of qundeatie terme inthe mucleat ‘soondiontes (FSF By). In dealing With the electronic ese we Mat, {for example, for & mole like bensene, make whole sei of fily Arasie approximations Pmt we consider the setron wavelunotion tobe mado up of molecular atital approsimation 1, then we restrict the form of the molecular orbitala (MO) to linea combinations af ‘stomie ectitals (approximation ), then we axparsto ot the Patt of the travefunetion coneemed ‘ith sls sed deal only with the {Feloctron part (epproxination 3), nally we solve the appropriate ‘Sostions By: making aawumptions about cerain integra over the ‘eletronie MOs (approsimation 4) The Sl step brings vt to the “Hickel moleclar orbital method, which a famine to all chemin ‘Symmetry eater the epprozimute solution ofthe slestonie Sebn®- Anger equation in to ways, In the Bev plac, the exact MOs are ‘igefunctions of wn operstor which commutes with all Oy ofthe point ‘rap concerned, they therefore goneratemeducble mpreveatations ‘ot that point group (ee Chapter 6) and can bo clued recordingly ‘The same is teve for the approximate MOs and conwoquently oo comstuota thom fom combinations of atom orbitals eymanetsy ‘orbitals whisk generat educa representations In the second place, the Hamiltonian opeestars which osour and commute with all Oy belong to the totaly symietric irdeitie ‘prematation T¥ (ace Appendix A103) and tagrala over them Sp'*Hiy dr vanish onles 17 T (oo oga (64.8). Tro, fm atrying (Out an approximate soltion of the eletronie Scréinger squeion, ‘hanging to act of baisfanetions which belong to Uh ieee epreventations wil allow a, by iapection to pat many ofthe atagral ‘which occur equal Yo zero. ‘Phore will ao, bear of thi, be a188 Maas rhea Thar Immediate factorization ofthe equations, Two example, enzone and ‘the tevinylmetl radial, Wl be conaiered in tall 182, Te MarvorFockaprsimatin ‘The stating point for any molecular electronic probleme the lectonio Seredinger equation: EEC, 2m) — BY 3, I thin equation H, the Hamiltonian x deBced by precae quantum tuechanical als and ona be writen in stone ite(Appendic A 10-1) an Wain $ $i ws whee eo aE te (0.22) Tnoqas(1021) and (1022) inthe numberof dectonsin the molecule + inthe distance betwen electron pana ltr », $$ ys a the ‘potential energy operator due to iterations between the electrons, ‘fin Laplacian operator involving the coordinates of electron M,VE a the kinaticenergy operator {in atomie units) for eletron ‘inthe dite between slocrony and nucleus, 2, i tho cargo on nucleus «and — 3 Aji the potentiabenery operator arising from th interactions af elacron with all the V nucle "Yi, 2,..n) tthe cletronle. wavefunction and expltly is a function af the ordinate ofall’ electrons; in this notation the ‘oordinator of given electzon are ajmbolized by «single number. {the total electron energy of the melecale ‘Tho Hartew-Fook (HE) method, or wif consistent Ald (SC¥) ‘method ae 1 le sometimes called, approximates YU, 2..m) By ex ‘rening it soldy in terme of functions each of which conta the ‘oordinntes of just one electron; these factors are called moteur ‘rae (0s). This nan approximation eens in realty the poation ‘tone seston ia always eoelated with the positions ofthe ote 90 ‘hat the fonction which dewibee given eleetron cannot be independ fut of the inotionn dweribing the ther slstrona Tt x for thin ‘eas tht the error inthe electronic energy in the HV approsietion ‘alld the oaraaton energy "The actoal way in whieh the MOs ar put together to form ce) | retried by to fundamental (One ix that an electronic Moloac nia Tery 198 vravefunction must not dstingulsh, by testing in a dierent manner, ‘he electron om amother;thsithelaw of ttnglababiy of det ‘al parila. The other ln i Unt the slecteonis mavefancion mount ‘Shange ite nign ohn tro lector are interchanged thei he ant ‘Symmetry ln and in fast neds to the Puli exclanon principe ‘Both those Inn ae aad y expensing (2) in tera of| the MOs with « Slater daterminaxt fey ec). Oat Jaxer oa). oc} YC, Boum) = Ayal = 0023) lam) 4m). O00) 1m thin determinant 44) symbolize the sth MO an e well-defined ‘inetion ofthe coordinator of slectron jy we aay that slectson jie ‘occupying the MO 0) Ifthe determinant Sa multiplied out there will be! terms and ooeh term coreeponds tone of them! permutations of then electrons among the MO; anc all permutations er inloded, fovery electron iz trnted equally and the indeingsabublty law In ites to slacrons are Intrshanged then, for Sater determinant, hin la equivalent to interchanging two rows and if two rows of «deter ‘ant are exchanged it changes ign hence the antinymmetry Iain alo ‘tied, og. if We exchange electrons I and 2, ve got lee) 942). 0) jam say. een) FEET m) = Ulva 0) in). Oat) fey 8a). @,0h) leur) 9a). O42} = AAIyat loin) 04m = v0.8.0 Fara n= ese.200 Matclar OntalTaay ‘That (1,2) nocsatly ants the Paul exslsion principe le (ridet from the fact tf two MOn se abwately dential Giheig ‘heir epin components, then vo are Cro columns i the Slater determt ‘Bent abd s determinant with te Hentoa slemna ie aero, ‘The iyi fasor preceding the devrminant takee account of normalization, ance ifthe MOs are orthonormal, this factor enaares Joffre 202m) ‘The way in which the Martewe-Fock MOs ae determined i by using ‘the variatlonal method, tht inthe fora ofeach MO la veri unt the toga fo SF YOU. IBV 2. mde dey dey ea Low a ali (024) ‘We will call the MOs that atiafy og (10-24) with sxpuc to comple ‘atntion in thee form the exact MOe ‘By introducing eg (10-23 nto a (10.24 3 pons to aire sta simplanet ofmonedaronegenvaive equation, called the Hartree GON) = 0K) FD (102) srhore He) (explicitly defined in the next section) a an effctive Hamiltonian operator tlated to Ht std involving the sordinates of levtton The eigenvalue ej ato constants called ert energie, ‘Once the Ms have Been found, the total elctonioenengy ie obtained from the equation: Bm fof ML Boe DHE. Bom) dry or ‘Since i can bo shown that HG), lke the orginal Hamiltonian H, commutes withthe transformation operators Og forall operations K [rte point group to hish the moleule belongs, the MOw aocited ‘vith’ s given orbital energy will form « function space whose bait fineraten& dfisteevedutbe repromntation ofthe point group. This {Hvesactly parallel to the ataation for the exact total slactroale wavefunctions. "The exact Os may therefore be clamifod noonding to the redacible representation to whieh they belong abd usually Uhe symbol fer the Teraduthe pronation (i lower sae type) i tad 0 aba the MO sth which i in amociatd. For example, forthe point group J, of MYO, 2, ardey deg) 0 Mole Obie Tory 204 sethane MO right non dageeat’e orbital or tp dagene- sont octal oe “ i 163, hecho Mo spreinaton Rather tan fad the moe perfect MOs which sty oon (1024) (cree 102.9) cmon pestis par th pret ‘Mechta faoeties of = rested natures Thess feeton il ‘rocrly conta stain parses which se then be opted in ‘Soordance with age (1020), Sce thee MOy tre ta om fern we wl ave atodaed ter spposinnton, te soe ‘che dtrned bythe depres of ety i far of Sota fonetone Mypiel of tle Lind ef pprosintien the ooo ‘ich expremce the Ipce prt of the Mos crews twat cob fone of tome obi sore on ha ste or feet si ho ‘oleae, We rit th pee pesto cach fhe apronnnte MO se 26) Zo (m= 2) (oa shar the 4, ar omic otitals andthe Cy ar inna coiceata ‘how 6 are called Linear Combination of Atomnie Oriel Molealar ‘Orbitals (LAO M0) andi thoy ae lntrodnd nt the Hartree Fook szuntions (equa (1026), «azple st of equations (Ue Hartron Fonk ‘Roothaan equations) i obtained which ean be ima to determine the ‘optimus coetiieta 0, For thon ayant where the space part of ‘ich MO is doubly corapied, Le. there are to sects in each sith spn «and ain Prpretively eo that the sonaplate MOslneuding ina dierent the total wavefunction ie YE 2m) FBC) (282) OH) Baal BLN he following equations: 3 Janae Semanssoune FTN een bs mi = f sranmerangsay an, ne Ba | sbi de moh Zuo ews done