MOLECULAR SPECTROSCOPY Brooklyn College (Ciy Uniersi of New York [A WILEY INTERSCIENCE PUBLICATION John Wiley & Sons New York « London - Sydney - Toronto595.388 oN cut -ti Mh cos Wn. 32 Conyih © 1975 by ab Wey Sos, ne ‘Avis eee, Pb loony Cana No to hk yt repo yA meas ot Toit wenlad not mucne nga tray of Cons Caegig Piao ss ‘Mace pec a Wiens pubnion™ ey. ei fhe oak previo pb 8.2 ators Quast hems soph acesematas srk Tes04r PREFACE This book is intended for graduate and advanced undergraduate courses in smolecuae specuoscopy. Il presupposes some knowledge of quantum ‘mechanics. such a5 16 guined in one-semester introductory quantut- chemisty course “Ths texts a much-evsed version ofthe book previously published 3s Volume I of my book Quantum Chemis. The fist chapter of the present ‘ook reviews quantum mechunics and atomic and molecular eletroni structure 0 that this book can be used completely independently of any other book [My alm in writing this book has been to give stents a solid under standing of the theoretical bass of spectoscope methods and an appecia- tion of how these methods provide information on molecular structure Brit descriptions of experimental specwoscopic procedures are also in sled. T have tried to present material as clearly and logically as possible, ving sulicient detain the derivations to make them easy to follow. The {ext takes into account the limited mathematics and pysics background of the average chemistry student. However, in no sense is the treatment superficial or "watered down” The major changes in the new edition are as follows: There ae three few chapters. Chapter Iisa review and summary of aspects of quantum mechanics and elecronic structure relevant to molecular spectoscop, This chapter replaces the chapter on electonic structure of polyatomic molecules that was repeated trom Volume I of Quantum ‘Chem. ‘Chapter 2 is sobstantally expanded presentation of matrices. Previously, matrices were covered inthe last chapter. The placement of matics ext) in the book allows thei use throughout the book; in particular, the vey ‘edious and involved treatment of normal vibrations has been replaced BY simpler and clearer treatment using maties. Chapter? coves molecu tlectronic spectoseopy, and contains two new sections, onc om electronic spectra of polyatomic molecules and one on photoeeciton spectroscopy, {ogether withthe section on electronic specia of diatomic molecules frm te previous edition. In addition to the ‘new materal on matics, electronic spectra of polyatomic molecules, and. photoelectronspecvoscpy, he flowing topics ave Been added ine with and hare Se Mees (Sexton 3, sin Felnation action 88), isin ins Fourier transform NMR, calulaion of Soetiients, orator trent soutien Svgave functions, Koopmans’ theorem. ab info and sxetedte,Cucutatons of nization polenta force constant, and imagncticresonance parameter: An hey the st chapter I tis desired to cover FOUR cessed the course, Setions 91-98 of the group-heory chante theory eas yr Chapler 6 on molest vibrations, and Sections So.g.12 readin conjunction with Chapter 6 yea sce Bolton and Harty King reviewed the mandscrpt of the Pe om of hs be have belately incorporated many of they nowt Suggestion iso grateful to Professors Frank sin this edition. Lam al ate rein Sando who reviewed an caer version ofthe present witb. Profewor Vieki Chuckrow provide sd helpfel advice on some cditon Mel points The help of Dr. Theodore Hoffman of Wiley: Tnersince is patfuly acknowledged thay suggestions that readers my Have bbe welcomed for improvement of the book will na N. Levine Sern CONTENTS (CHAPTER 1 QUANTUM MECHANICS AND, uw 12 3 14 Is 16 i 18 19 110 121 ELECTRONIC STRUCTURE (Quantum Mechanics Mathematics Review Unite ‘The Particle in a Box ‘The Harmonie Oscillator (Orbital Angular Momentum ‘Angular-Momentum Ladder Operators Party ‘The Variation Method Perturbation Tory ‘The Cental-Force Problem The Two-Paticle Problem ‘The Two Particle Rigid Rotor ‘The Hydrogen Atom spin “The Pauli Principle Many-Hlecon Atoms Symmetry Point Groups Molecular Electronic Structure The Haree-Fock Method Seniempiicl Methods soeessstsegneeeraeeseCcuAPreR 2 MATRICES 2 Mates 22 igenvalucs and Eigemvecors 23 Matrices and Quantum Mechanics CHAPTER 3 TIME-DEPENDENT STATES AND SPECTROSCOPY 3: Time-Dependent Perturbation Theory 52 Absorption and Emission of Radiation 33 Selection Rules 3A Spectroseony 35 Line Shapes and Widths 36 Lasers CCUAPTER 4 VIBRATION AND ROTATION OF Tem TOM MOLECULES 4.1 Nuclear Motion in Diatomic Molecules {42 Anharmonicty, Vibrtion-Rotation Interaction, fad Centiuga Distortion 43° Potentia-Eneray Functions for Diatomic Molecules 44 Selection Rules fr Rotational and Vibrational Transitions 45 Rotational Speta of Diatomic Molecules {46 — Vibration-Rotation Speetra of Diatomie Molecules 447. Parity of Diatomie-Motecule Wave Functions 48 Nuclear Spin andthe Paul Principle 49° Ortho and Para Moaifcations of Homonuclear Diatomic Molecules 410 The Raman Effet 411 Rotational Energies of Now! Diatomie Molecules ry a 10 18 165 168 us 1% 18, 186 (CHAPTER S ROTATION OF POLYATOMIC MOLECULES. 5.1 Nuclear Motion of Plyatomie Molecules 52 Classical Mechanics of Rigid Rotor 5.3 The Rotational Hamiltonian Operator 54 The Spherical Top 55. The Symmetic Top 56 The Asymmetric Top 57 PureRotation Spect Polyatomie Molecules 58 Mierowave Spectroscopy of (CHAPTER 6 VIBRATION OF POLYATOMIC MOLECULES, 61 Introduction 62 Classical Mechanics of Vibration 63 Symmeury and Normal Vibrations {64 Quantum Mechanics of Vibration {65 Selection Rules for Vibration-Rotstion and Pure-Rotation Transitions 66 Infrared Spectroscopy 67 Raman Spectroscopy 68 Degenerate and Near-Degeneate Vibrational Levels 69 aiy of Polytomie-Motecule ‘Wave Functions 610 Nuclear Spin and the Pauli Principle CHAPTER ELECTRONIC SPECTROSCOPY 1 Electonic Spectroscopy 12 Fleewoaic Specta of Diatomic Molecules 73, Blecconie Spectra ofPoyatomic Molecules T4 Photoslecton Spectroscopy Ws 7 203 210 a3 216 29 296 a6(CHAPTER # MAGNETIC RESONANCE SPECTROSCOPY BL Magnetic Resonance 82 Nuclear Mapnctic Moments 83 Nuclear Mapnetie Resonance fd NMR Chemical Shifts ES __NMR Spin-Spin Splitiags 6 NMR Spectra of Nuclei Other Than Protons £7 Origin of NMR Spin Spin Coupling 8 Spin Relaraion £9 NMR and Rate Proceses 1.10 Nuclear Quadrupole Moments LIL Electon Spin Resonance ‘CHAPTER9 GROUP THEORY 91 Groups 9.2 Multiplication Tables 93 Coondinate Transformations and Mawrices 94 Representations 95 Character Tables 916 Basis Functions 9.9 Group Theory and Quantum Mechanics 98 Group Theory and Electronic Structure 99 Group Theory and Molecular Vibrations 9.10. Group Theory and Molecular Rotation SLL The Direc-Product Representation 9.12. Character Tables of Some Point Groups ANSWERS TO SELECTED PROBLEMS inex seezes 4 geese m 5 pereren emua MOLECULAR SPECTROSCOPYcurren | a QUANTUM MECHANICS AND ELECTRONIC STRUCTURE 1.1 QUANTUM MECHANICS Betorebexining ove study of molecular speccoscopy, we sal hia tae sevew and summarize thne specs feasts ene omic and mofsylar clectronic ste hat ae elon ‘pcos Sn wun il ert mc in quantum chemistry, we sil 80 Be dened nero coe chapler If the reader pure by any a ese Gan cons Levin Ga, ilar o Ping and Wiber fo ed (Bferences withthe authors mame aed we ae eS Bblgspy.) Rath: than going rough Cape Ln doe i 8 sini and eer back wa Sed ah shapers > STE Dai ot ede when ring Th sae of a wate Quani-echanicl nem i dserbed by x ate ficton MG, whee ¢ Symbaize te Bn aaah ae oninaes ofthe prc, and? the tine The fea a Hielevaled and continuous addlito, for Ree ma Seats inteabeby ths we meat thal JPOP ee (de dense inteatoh overall sce ech ‘conditions is said to be well behaved ‘To each physical property of & quantum-mechaicl system, here cor retponds 4 quantammechaieal erator The opera foneed ay2 ena Mechanar ice taking the casia-mechanical expression forthe property and replacing rc econdinate by the opeator multiplication by x, and each hear momentum component, bY the operator (h/748/ 3x). Using & ‘Sreumfler to denote an operator, we have a ay where Aahle, ‘bing Plan's constant ei ice operaor corresponding to the physical property A, then any memsaremet of the property 4 in any quantum-mechanical sytem must cease thal i one of the eigenvalues of the operator A, The erences a, and the epefuncton g of Aare defined a those numbers Sind functions that sts dam a «sy It we tke a large number of ifenical systems, each with the same state uncnan and case Ain each sytem, We shall in general get different aetcinciferent systems, (This oe of the striking diferenees between renal iad quantum mechanics) The average eahue of A, denoted by ‘AD postulated to he given By aa cays feria where the integration is over al space and ¥ is normalized (To find (A> wReTimenaalye we average the ress of separate observations of in a sige nomber N of Mente! systems, each in the same ste: TS ner the sum i over the observed values 4.40, Tis fant equation is equivalent to y= Brae where the sum is overall posible values of 4, and where P(a) isthe ‘robabitty of observing the value @ forthe property 4] Sn it which te state function ¥ changes with time is postulated £0 sscinceaeecaaaneneeenleaieememmaaaeeeneal 1 emma Mec 2 be given bythe simeslpendent Schridinger equation 1h ay say as vere Hi the Hamitnian (or emery) epeatr for the sytem: fi bined by converting the classical mechanical enresvon forthe ystems nergy in terms of Cartesian coordinates and linear momenta t0 aM fpeator by the procedure desribed above. Thus for 2 onepartise ‘three-dimensional system, the classical-mechanical Hamiltonian function i {he sum ofthe Kine energy T and the potential energy 1” Mats Y= (Rg Ap) Ams Vessret) i) where Poi P, af the Hnexrmomentum components [Equation and the potential energy is defined by ts we) “Wank, -W/y=h, —Wieek, 19) where FFF, are the components of the force on the particle Replace ment of elasial quantities by operators gives asthe Hannltonin operator £(2+5 SE) ero 0 # Sit aa fin evra v(s nish A) us whee 9? 93/224 32/2924+2/ "isthe Laplacian operator. For an ‘a-particle system, the Hamiltonian is ‘ai me fs AD Ete vesntieo 1 oe as) a) VP O8/anh Jay? + 02/2 (119) ntgeation of (5) with respect to time introduces one arbitrary constant. If we know ¥ atthe present time fy we can evaluate this constant and thereby determine ¥ a any future ine ‘Quantum-mechanical opeators that correspond to physical properties smut be linear and Hermitian, A linear operator 4 sais Afra) ated Ahmeit aay an)‘ enum Mesh an tae Serre where fang are any fonctions and ¢ i any constant A Hermon peor va et operator that sss Jricar= falda os) foe all wlibeaved functions fang, whee the integration is oer al space wi eigentonctions of Hermitian operator fxm a compl et. By ee eet anywebchaved fonction J that seis the same TMesndary conditions he cam be expanded at so Daw (a) where the expansion coefficients ¢, ae constants he paceeding siemens together with the postulates of spin and the paul prinaple (Sections 119 and 1.16) can be taken as the postulates of ‘quantim mechanics. he petental energy V inthe Hamiltonian is independent of time then there ens solutions of (1S) that have the form Hans (13) where fi 4 funeton of time only and ¥ i a funetion ofthe coordinates Waly, io veety(L15), we submtte i nto (15) 10 get —0/ 0/0400) omtintiytay. since Hf doesnot affect J). Division by ives asin, va) 70” Va Since fis independent off the sight side of (16 is function of the SeSlitates only while the Felt side isa function of only. By the usual SShuraton-of-warables argument (Section 12), each sige of (1.16) most cen antant which we call E- Therefore, ~(A/iMd/)/S= , which Saethsues to f= expC 11/8), where Ais an abiteay constant. Since ete abuorbed int the Function vq in (115), we drop i 10 ve poem ay (116) [so we have iy /y= E oF fig= 60 cs) whichis the timeindependent Schrodinger equation ce tanion” Sine the Hamiltonian operator Fis formed from the simply, the Slré- 14 Qentum Mec : clasial-mechanial expression forthe energy, we have B= fl. The num: bers E in (18) ate the eigenvales of the energy operator, and by the postulate preceding (1.3) the numbers B that satisy (1.18) are thus the posse enerpe of the sytem. Sats ofthe form (1.15) ae eld Hane") 19) the energy ofthe state and isthe wavefunction. ‘Common notations forthe integrals that occur in quantum mechanics Jardgar= ll = Gdlp =. (120) where g, and ate Functions, d ian operator, and the integration is over all space. The integral sm (120) i often called a matic element A.A notaion used when no operator occu i the integral ie ay Note that A (12) Te Hermitian propery (113) expres in bachet notation and in caldlgy=Codlny® (123) Ant (128) Ket notation is sometimes sed fr fant tions in quantum mechanics. fn this notation, the funcon fie denoted by the symbol [P. f=[/> Ket oation is eonvenint for denoting eigenfunctions by sting ter sta tex Thus) denotes the hyrogenatom statonay-tate wane nein ‘th quantum numbers abd The following properties of Hermitian operator follow from the dein ion (123). The eigenvales of Hermitian operator are wal Two ge. functions of + Hermitan opeair that corepond to dicen sigenvales are orthogonal that is dis Hermitian and dp, = aypy, dsp mith aye then tee insets «sleds [otoad (125)‘etn Mastic to Beck Some The commutator [4,8] of two operators is defined as aa ° (139) we say that dnd B commute C90 Hermitian operators 4 and ceed ita be proven tha thee exe common complete eof aoe eee thems that H (139) holds where A and 8 are Ferre ten we erm find some complete st of functions sch that Fan cy one oF more of the egenalua of A are ere ce Wve i element of choice ia that we can take many depen, we hae ston of the cignfunctions oft degenrate cer car ae ue tncarcombmatons need be eigenfunction of Tentven the theorem docs show tht we can choose near combination ao as of The converse tthe preceding theorems aaa pene bare nar opto: tnt pouess common comple 12 pento ten and Fonte Fre or mr ope Seamus commie for tee to exit comple st Fe ee mon 1 al the operators Thos 4. and C bave 8 wt and only LAO. (4c Stenuncton Seton completes of estudio tu ceo 1s he inthe sae ¥ at some nant of tine. Lt be te coca numa penne oe Herman operat that corresponds tothe physical property G: Ga= 8m apanding ¥, we have from (130) and (1.33) ¥o Zann Lae, (140) Substitution of (140) ito (G)=HIGIW) and se of orthonormality gives <@>= Diels, any 1 ems Mectanr . However 8 ted eatin, we have =D Pade 2) ‘whete P(g) isthe probability of observing the value, for. Hence we conclade that PUal=laP Kee! (143) “Thus the squares of he aol vals of he cota in the expansion (i give the probes for observing the various posible valves of the phos! proper GfFor the special cae whee the state function tcenfuncion of. ¥=yy. we have oy=t in (Lal), and we ae cra 10 “huere gy im 8 measurement of Thus, for saionary state, we have GVW EY, and an every measurement certain to ge For 3 propery with continuous range of allowed values (8. 2) 1} becomes cae fried cay were P(4) i the probably density for property’ that, Pade the probability of obsering a valve of G between — and q-+dy. Consider 4 ‘ne-particle, one dimensional system, From (14) with =x, we have Jvenvdr= [7 Weds ass) Comparison of (44) and (145) shows that |¥ is the probability density for the coordinate; that i, the probability of finding the particle between pes fae uppore that state function ¥ at ime (ig not a eigenfunction of G. Let the eigenfunctions and eigenvalues of G be 9, and g7 Gy=Km% A measurement of Gat ime , wl give one of the eigenvalues of G. Suppose te find the value g,- For a measurement to have any meaning, it ought 10 be repraducbl; that i if we immediately remeasure Gata time f, bd {hat difers from 1, only by an infinitesimal time interval, we ought to gt ‘my aaain, But the second measurement is certin to give, then the sate fnetion at time 4 +a must be gy, the eigenfunction of G with eigenvalue ‘. We conclude that the measurement of © at time fy changed the state function from ¥ (which & nol an eigenfunction of G) toy the een function of G that coresponds 10 the observed valve of This sudden ‘change i sate function caused by a measurement is called the reduction of the state function. Note that reduction i 4 probailtic change, since Wecannot predict wih certainty which eigenvalue of G wil be found by the ‘When ¥ is not an eigenfunction of 4. measurement of 4 in ideniat stems each in the same state ¥ gives various values Asa measure of ae spread in the observed values, we define the unceraiy for stndond dlevaton) AA by (a4y'= (4-il(¥d. ay) aan Which isthe general statement of the uncertainty principle, For the ease Ams Bp, Eas (LD). (12) and (14) ive (Ads ia amin (14) xp, 21h (19) ‘Thete also an uncertainty relation involving energy and time: aerodn (150) In this elation, BE is the uncertainty inthe energy of a state whose ttm it. Eguation (1.50) 8 ota special cae of AT. eth, (10) ‘st be derived by a special eatment [See ¥. Ahavonov and Boing, Phys Re. 12,1689 (1961)] Consider the mati element (qld), where g, and g are cienfune- ons of « Hermitian operator 4 that commates wih fey dy =a and (4, F]=0, Then, provided the eigenvalues a and g oe fh ‘avai Tolows Problem 13) that Cdl vane: Kaldlg>=0 itaee, ash) From (1.3), we can derive a useful sum re. Let and S be any two well-behaved function, let 4 and be linear operators, and let es ‘complete orthonormal set of functions. I we set f= BS i (13) avd ses 12 Mathematics Review u operate on both sides with 4, we get Ais Solis >4q, Mulupication by R* followed by integration over all space gives the esiced sum rule TeRldlar= (19) 12 MATHEMATICS REVIEW In this section we review some mathematics useful for quantum chem isuy and spectroscopy. Vectors. 8 physical quantity that has both magnitude and direton can bbe represented by 1 directed line segment a vector in three-diencion Space Let A be a vector quantity. (We use boldface type for vectors) We Sel up a Cartesian coordinate system 192 and denote vetors of unt length slong thes, ands axes by Land , respectively It, and ate the projections of A on the x,y, and z axes, then A is piven by AMAL ADA (133) ‘The magnitude of Ais 4 IAl=(ab are any! a) Since A is completely specified by the three numbers 4, 4, 4, we can regard a vector in threedimensionl space as an ordered st of theee ‘number; thus the vector (2.0.3) hasan x component of 2 ay component ‘of 0 and a z component of 3. [More generally, we can regard an odesed Se of numbers (AAA) a8 & ¥ecor in an abstaet nedimensional “space”; an n-dimensional vecior space is 4 mathematical concept athe ‘han a physical one (unless <3] Equality of vectors means equality of heir coresponding components. f A&B, then 4, By- =, 4, = 2, The dt product A= B of two vectors given by ABOAD 48448, BoA (155) 4n particular ACh Alea ASIA “The dot product can be show tobe «selar equal to A+B=|Aj[Bloos0 (136)2 (Geno Meche ad Hn Sra vwhete is the angle between A and. The cass uaduss A x Bs ven by A B= (4,8, ABA BAB IHALB, ABR (LST) hich is most easily remembered in the form J A A, } “be sale 4 4 BB, , B 45 as) (Dutceminants ave discussed below.) The cross product ean be shown tobe SNector of magnitode[AlBfsiod (where @ is the angle < 180° between A {Ind B) and direction perpendicular to the plane defined by A and B, such that A Band A'x B form a righthanded system. The vetor operate W (del) s defined as L V =10/ax+)8/ay +ha/e (159) ctr. An operator isa rule for ansforming any given fonction vo sone her Fenelon I he operator 4 transform the function ft the Fenton swe write x=-4/ (where the circumflex denotes an opal “The tu Sod the psc wf any S40 pets are defined by (4+ BDF Lis Brand (ibys a( fi). Not that Bf some funtion, and apy ine fo Bw ele function delined ts By. Two operator Aad equal APB) fr al fonconyf The ml aerator 0 ad the wit Sperar Tare dfied by 0/=0 and 1. [Noe that (1.48) and (139) are Soe precy weiten sb |= ni (1.0) liad as) However we shall usualy omit cirumflexes over operators that are simply tmulplication by a constant] Repeated application of the definition of Uperslor mulpication shows thatthe associative law holds for all ope Aaey=(4 (0) “The commu [4d of two operates dfined by 4.8) The square o AB defined by 4° = 44, with ima Qin La igen and g and all coastans cA Hermitian operator i linear operator that ‘obeys (1.13) forall webehaved functions f and g The eigenoales and eienfinctons ofan Operator are defined by (13) ‘Some identies vali for linear operators ate (163) (164) ss) [A.B )=[4.kB |= 414.8] ea const) — (168) Liar e114 14.6) (un La. 8C|-[4. 816+ 84,6) (168) Uad.e 14. C1 + 418.61 (109) TF complex munbers. A complex number £ has the form 2= x+y, where = VT and x and y ate real numbers. We can represent «by a point in the complex ay plane by asrociating the complex number = +p with the poimt whose Cartesian coordinates are (x). The distance r of the point: trom the origin is the absolute value [of 3 the angle @ thatthe Faulus vector from the origin to 2 makes wilh the postive x anti the ‘Phase of 2. We have leet, tanday/s (1.90) mreosd,—y=rsind « pet b= rl cos0 + sind) «ny bere we used et mconb ind an) From (1.20) and (1.72), follows that 24 “The complex compat z* of is defined by Bastar yy 78)“ ‘cum Mahi so Ete Smtr We have entities are 1 if and only if zis & teal number (with y=0), Some a tayteraleh 079) (ea) ate Let o*= 1, whore is postive integer. The e001 of this equation are heath ros of unity The number {has absolute valve 1 and ts phase can be taken an 0 of 29 or dn oF 6 Of wn. Hence Ime, where & wed Ite take the number e**/" and ease it othe mth power, we pet (olay, Hence the mh rots of unity are nol beVET (178) (ih ken ye we ge the sme LOOK as with K=O.) 1 Determinants determinant of order mi square array of cements the determinant has a value calculated BY the procedure desribed below. 1G be the element inthe throw and jth column of the nh order Usterminant 4. The minor of element a isthe determinant of order n~ 1 ‘Stained by striking out the throw and th column of 4. The eofactr Cy fof ay 1 its miaor multiplied by (—1)*7. When n>, the value of the eicfainant 4 i obtained by taking the » elements of any one row (or slumn), multiplying each such element by is cofactor, and adding the m products Thus if we ae the elements of the Kth row, we have Anat tnlat +uCia™ E ainCin (LT nherek can be I or 2.0¢ ++ oF a: We have thus defined a determinant of Ucn in terms of determinants of order n~ 1. A determinant of order 1 acoog element and the dterminaats vale defined athe value of chat Clements ths [_sl=—S. where the vertical lines denote a determinant (Gul notabgolue Value). Fora detertinant of order 2, use of (1.77) with Kal gives fu) aylanl~auleal=auea-anty (1.78) where the vertical lines indicate determinants, For a determinant of order 12 Mahe Ren ts 23, use of (1.77 with k= 1 and (1.78) gives “The principal diagonal ofa determinant is the diagonal that cans from the uppe lett the lower right. A determinant isin agonal form when ts only nonzero elements ie om the principal diagonal. A determinant block-diagonal Tort when it only nonzero element ie in square blocks czntered along the principal diagonal ‘Some theorems on determinants are the following (1) If all the elements in any one row (or any one column) ae er, the determinant equals 20 @) Interchange of any two rows (or any evo columns) multiplies 3 determinants value By ~1-(3) If ay two rows (or any two columns) are denial, the determinant equals zero. (2) Mulupication of every element of any-one row (oF aty one column) by the constant K mltpies the ‘determinants value by k (5) Addition ofthe same constant lip ofthe tlements of one row to the corresponding elements of another row leaves {he determinant unchanged in value. (The corresponding statement holds for columns) (6) A determinant in diagonal form equal the prodvct ofthe diagonal elements. (7) A determinant in blockdiagoral form equsls the provlct of the block determinants, For example, we 000 br ooo Pan oor e cht le mo] uum oom mrAlli We yy oO e rr Simuitanous linear equations. A set of simultaneous linea equations in the m unkown yoo ty has the form aysyhatet taney ayes ata Hae (130)“ ena Messe a Herne Ste ‘where the a's and b's are constants, If by=by=-+- = by=0, the st of Chuations a homogeneous a least one ofthe B's is nonzero, the ses ‘homogencon, Lat det(e,) be the determinant ofthe coefficient in (1.80) deiy=|" om oan) Let, be the determinant obtained by replacement of the elements of Column it det(a) ith byPysnPye Cramer’ rude states that Torin Homogeneous equations, the unknown x, is piven by at (12) Ase near Homogeneous estins nm wnknow lays has the so ae eee, whch the ila salon, Suppose the ‘uti aetcmimus det.) ot cal to eo fr ast ot Ucar Herre stmatons: we can then wee Cromer rule (82) Since the aaceraarehomogencou the determinant Ry wl fave a ealumn of ‘row and wil ees ee: eee , and we hve only ea Tousen ‘The fr a aural slaioa ofthe homogeneous RAR ens we most have dl(a)=0. Ths condivon can alo be GRUPOS Saisen to insure the exbtence of «noni sein, A seen dlanouy, ned; Bomopeseou equations in w unkown PET astcivt slum i and nly fhe determinant ofthe eolicents caual 0 igen dys wn of «tf at ame tl edo hen eddy ey (here € 1 any con Sip stay acento be a sobtion aio Since we have an arlary cae ihe lltion solve set of ines homogeneous equations we eRe he unknowns (ease) ua tam abray constant aye), cae oe iy the equtions tn equations in 1 unknowns we Bee) Gite ang proceed to ve the set of n— I inhomogeneous Seen ee Mtatmonne, {be mow efficent way to do ths By Sears acon of unknowns ater than by Cramer’ rule) In SESUuT sedhnie the arbiwary constant c usally evaluated by Sormalzxton Linc indopendence. These of Taneton fff sd 0 be Kina inkpenden ifthe only way the equation eat esto th (13) can be satisfied is with yey 0-0. IF the funetions fmol ate Tear dependent the (183) holds wilh some ofthe e's being nonzero Ths meant we ean solve (183) forone of the (sand expres it as. linear combination of the other members ofthe set. Fora linearly independent Setno member ofthe st can be expessed as linear combination ofthe ther members Talon veres, Let fs) be a tal function al of whose derivatives exis at the point xu and within some neighborhood of a. Then f(x) can usally be expanded! i an infinite seis (called a Talor sere) a fllows se oD Nea im Le) Hoy=flay (ay ot (1s) where /(a) the ath derivative of f(x) evaluated at pe] = [Tere area few exceptional cates where ll the derivatives exist, but the “Taylor senes does not converge to J(2)] The series (188) will converge ‘within some interval a-cexcate (136) centeted about a, and diverge outside this interval. To find the interval of Convergence fegufes that we consider J as function of the complex ‘arable =the constant cin (86) equals the distance from a tothe nearest Sngularty off) n the complex plane. A singularity isa point where for ts derivatives do not ext. For example, conser the Taylor-seres Expansion of 1/(L4 22) about a=0, The fonction 1/(1+-2*) ha sng ties at e= + and ~/ (where f becomes infinite), and the distance Wom a to the nearest singularity is thus I: hence e=l, and the Taylor sees converges im the imterval —UH)/ (iit independent of, Hence Fy independent of al the coordinates hd ia constant We have Fig dad= Ea) (4.106) which is Schedinger equation for partie I. Similarly, Higpha= Esbaad, + Hata Q)= Eatelte) (1107) From (1.106), (107), and (1.108), we have Ba Bt Eyt tk, (1.108) “Thus the wave function of a system of noninteracting panicles is the proxict of wave functions foreach particle, and the energy i the sum of ‘ners fr each particle. ‘The same reasoning applies 10 a one-particle Hamiltonian that isthe sum of tems that each tvolve only one coordinate: H= Hl, +H, +H, Here Y=EOWONED (1.108) BAB AE, (.n0) Hien Ete em By By rhe chain rae. Lat J be 8 function of x,y, and 2: = flxy.2). Suppose we cary out the following change of variables EN, (LI) (rn verted, ener) Substation into f converts it 40 a function of the new independent vaables 3, and 1 Sosy “The chain rade elates the partial derivatives of 10 those off (2). (8), om a Al(rsth yrs Hrs0)=a(e50) with similar equation for (25/38), ad (8/20), ‘Spherical paar coordinates. The spherical polit coordinates 1.8.9 are ete by drawing a taius vector Teom the origin to point (xe) 8 the angle Between rand the positive 2 axis: ri the dstance of (2). Irom the oniin; the angle the projection ofr in the xy plane makes ‘with the postive aus. The ranges of the vanables are Orc 20, OC 8 Si, O1 where 1s the length ofthe bor. The stationary-state wave functions and merges are found from the timesindependent Schrodinger equation. Ov fide the bo, the wave function must be Zero, because Fis infinite, inside lhe bos, where V0, the Hamiltonian i ~(F/2mbd*/ds, and the ‘Schrdinger equation i (8 /amyd¥y fae = By (112) Equation (1.122) can be putin the form (1.97), and (199) gives as the ener voluon | y= Acos{(me/W Ye] + Bsin [mex] (1.123) Since yi 270 outside the box, ory 10 be continuous, the funtion (1.129)ea Cents Messi so Beck Scr must vanish at the ends of the bor, x=0 andl: The condition ¥(0)=0 se ian nly he sine ter in (1.123). Fo he condition 40)°0 eae te ceroment ofthe sine uncton must equal me at =, where reese MNegatve values of mn do not ive lines mea Gide bo 0 everywhere) Hence B= 9?h/Sm. The con: solutions ermine by normalization. The allowed wave functions and tneries are then gee Q/n)Psin(mes/, O8HSL (1) 23 (1125) B20 (Sa iat particle ina bor 1a analog of the oneslimension ‘and; we have [A threedimension paricicin a reclangla paraleiped with ies dy o< yao for the region 06 x< 05 V. Quantum mechani tally, there i some probability for finding the particle in clasclly forbidden regions where EV. For, the three-dimensional harmonic oscillator, V= 4k,2? +4404 14,25 Separation of variables gives the wave Tunction The prodict of three one-dimensional harmonic oxilatr wave functions ad ret the eneay a8 B= (0,4 Hho +0, +e, +64 Ho, (1a) a2, 116 ORBITAL ANGULAR MOMENTUM bet be the position vector from the origin to particle in motion; let be the partici’ velocity and p its linear momentum: enabtyjt ok (11) V5 t/t = (de [dt (ay fa} r(de/ de — (1.18) Pe m= me,-+ mej + mak (14) were m isthe particle's mass, x,y, ands ae its coordinates nd b,j and Kare the unit vectors slong the ates of a Cartesian coordinate system (The Partcle’s acceleration a is @=dv/dt=d's/dr®) The orbital angular momentum Lo the particle defined byok herxole yz (1s) pm ~ Me bmapy ye, (1.146) “The square of the magnitude of the orbital angular momentum is BaveLeBegen (ua)a Gen Meshnis td Htne Strue Replacement of classical quantities by operators ives inya/az—23/) (1188) in(ea/ae—s0/2) (118) ipa ~iMad/ay—ya/0) (19) Deitsien (usp One finds the following commutation relations 10 hol: [ene ]eind, [iilemin Ube Jani, (4152 (adelASl Ale os) Hence there exits «complete set of common cgefunctins for £? and eee etrponen, The sgevalue equations for Land Z, are ae or rable im spbercal polar coordinates (bt notin Catesin roam the cain rae afore the eivatvs we can ind and En sph polr cori, and then we (1.150 tnd £2 One finds i= —ino/ 9 (1154) pre-r( sear, 3) sew Breed ot (135) e ¥( coe 00 sin? ag" Zand, have more complicated form than Z, but ao invave ony thd, and ot Te ar U8), (L113), and (1158) shows that the one-particle kinetic- energy operator can be expresed a8 w (a 29), 1p re Hal Sa 7 oa eu Let Y(@p) be the common eigenfunctions of £* and f,. To solve ity may, LLY ~bY (where a db ate the eigenvalues, we try a spare hon of voribles, writing Y(0.g)= S(@)T(9)- Solving the differential equa 14 Orbe Antr Monet, » tions one finds tha the well behaved, normalized solutions are Tale) Qa) Fem (ist) t+) imp |” san | tn) 9 LAH Ohl Me where the astocated Legendre functions Pw) ate defined by ayn dish oy ae ee cant ae cael a “The eigenvalues of £? and Lae found to be 14-1 and mh ep tively The anglaramomentur eigenfunctions Y"0g)= Sa @)Tot) ste spherical harmo sm 24) iy” E,YP(0.9)= maY (8.9) (1.162) The eigenfunctions 97" have been normalized: moreover, being egenfene tions ofthe Hermitian operators £* and Ly they are orthogonal; hence [FC [ferro ve ersinnatty hue (118) ‘were the sind factor comes from the volume element (1.114) "A moving electric charge generates & magnetic field. For a particle with charge q and mass m, is orbial angular momentum L gives se ‘magnetic dipole moment, given (in Gaussian units) by m=(a/2me)h (1.6) where cis the speed of ight» uns Mesh ad tn Sere 17 ANGULAR-MOMENTUM LADDER OPERATORS. “The lst seton dicesed angular momentum from the ewes af we ie erent egenva equations ha sult fom expressing ae ie iferential operators. The ladde-operator approach uses jst ation eatin, and abo appliabe 10 the angula-momentam comme {he a ae cn 113) Rater than wing we sal we San an ence tat weave dain With any Nd of angular verte even thre Kinear oper atc commutaton ats [ (1159 tors S.A, that by hypothesis bey [sts =init,— [MitJ=init [Mat ‘he AF operator is defined 2 spose sige se (1.166) 1 follows from (1.168) and (1.165) that [oa] -[se.a]-[ a4] =-0 (us) vo hat we can hve siutaneou eigentunctions of M7 and Mt SP g= Ym Ye Pala (1168) “where oan bare the eigenvalues, ad Yq (0K necesaily the spherical harmonics) are the common eigenfunctions "The raising operator M7, and the lowering operator hate defined by Gentil, ahi, (1.169) From (1169) and (1.165), me ind hat (6. Yn) =n MM Yon) 4.170) M54 Yn) =(02-MM Ye) un 1, 104 en eigenen Yu comers it oan so that spptiation of ee ith cgeaale higher tan tha fq; MT Fwess igenunetion of M, wil 17 Angee Moma Laer pean, o the Mi, eizenvale by h From (168) and (L167, we find that (0) of Yh SUSY) (MY) (1472) so that Yq and FY are stil egenfunctions of 7? withthe same cigenvalue' 88 Yq. From (1.170) and (1-171), the eigenvalues of Mf, for 8 tive 4 ate spaced by ‘Using Side = SP 8 (7) and (1.168), we get (8-042), DY (ra) Since 2+ Af? a nonnegative physical quantity, it eigenvalues 4 ~ 42 rust be nonagatve: therefore ~o!/?< by cm where By i the rue ground-state energy. IF is not aocmalized, then (0.184 ie replaced by W = Calilin)/> Ee (1.185)‘A til variation fonction 9 thus provides an upper bound for the round: ate energy, Oe suas inchade variational parameters in and looks for thon valves ofthe parameters that minimize the variational integral IW the fonction then serves as an approximation tothe ground-state TN pec te of variational function is the linear variation function. Mere, has the form prehbedhsten toh ~ Sah (1186) snnre the funstions fev-fy ame linealy independent well-behaves Functions and the parameters cy. age numbers chosen to minimize the vanational integral HY Substiatng (1.186) into (185) and setting GW Jagd Gmina) so as to minimize Wwe are led to the Following Sct inet, homogeneous equations in the m URKROWRS 4.6 Sle -sol-0 1 (187) Hy= fatigan sy= fig (188) For a nontrivial solution of the equations (1.187, the cosficen de termina must vanish (Section 12) Hence (1189) Hy SQW Ha Hy SW Maa Sa =o (1190) My-SaW— Hg Sa “The seer equation (1.189) isan algebraic equation of mh degre, which swe salve forthe rots Ws Wye MS Way 9) 1 cam be peoven that these roo are upper bounds forthe true energes Eg aby. of the n lowest sates: 1M. (192) ES Woy BSW oe Pein Thy * Having found the roots (191), we subtitle them one at atime into the set of equations (1.187), which we then solve forthe c's; For each root Wie we find a st of coeficients cf. where the superscnpt indicates that these coufficients go with the root IW. Use of there sci of coefficients in (L186) provides approximate wave fonctions for the lowest tte, PERTURBATION THEORY Pecturhation theory is am approximation method useful when the Mam inonian Hof the sytem is “clone” to the Hamiltonian A of a system which we can solve exaely, We call the system with Hamiltonian Hf the perturbed syste, and the system with Hamiltonian # the unperturbed ‘stem: we define the perturbation Has aia (199) The Schidinger equations forthe unperturbed and perturbed ysems are ave fine, (uss) eae (1194) here the subscripts indicate state of the unperturbed and perturbed ‘ystems. To aid in relating the solutions of (1.198) to thos of (1.194), we imagine ‘nat the perturbation is applied in a continuous manney; this orvesponds to the stroduction of parameter in (1.199), 30 That iim feat (1196) ‘As A increases fom 0 tI the unperturbed system i ransformes into the perturbed system. The presence of 0 makes the eigenfunctions and ‘itenvalues of H depend om the parameter XY, ¥,(4:0) ad E, = £0 ‘where g symbolizes the coordinates, We expand y, and, a» Taylor series Jn denlig the cveficents of suecesive powers af A by YMA ad MED. AVP eID AYE (us) Bon EM ENED ENED (1198)x» emt Mech md tne Ste Not tht in (1197 we ae ase a iy 92 Howe 42 deers dezeacate enerey level any linear combination of the eon sed kGtunctons ofthe level sam egefunctin of 1, and we See eey. equal to a linear combination of the unperturbed Tletoes ine degenrate lec degenerate perturbation ther cee ee tyson, Tor tows we comer ony nondegenerate level The parameter A is just a mathematical device, and we ultimately set (1199) i= Eta leads tothe following expressions for” and the fist and second-order energy corrections LAWL? oy (20) BED Epecgeynm (20 on KOEI WOE 0 2 am where the sums are over ll states except sate vreaae a the dilficlty in evaluating the ifnite sums needed to find EONEO ome sometimes uses a uriaon-perturbation approach, in hich £2,600, aye evaluated by looking for functions that minimize ‘Telan itegras involving 7; see Hameka, p. 223, for details. ‘Now conier Perturbation theory for an unperturbed energy level that in fold degenerate, with the states fete (1208) Ef Any linear combipation of the m degenerate Jncuonst (203) isan eigenfunction of Has +0, each of the 9 pevtrbed wave functions §) (= l,m) that correspond to the fold Fefenerate unperturbed level will go" over imo” some particular Tinear all having enerey 10 Pertain Tey » combination ofthe function (1203) Bn Seat =o™ (1208) here we wsed gto denote these corer zeroth-order wavefunctions: ‘which ate the ‘creel zeroth-order functions depends om M7. (The J Subscript im cy indicates the set of coctiints for yi") Substitution of (198) ad 1.197) with 4 replaced by 4f into (1.195) leads to the following set of linear, homogeneous equations forthe coeficent fin mation (1205) ee] Ha = STW) (1.206) [The Kronecker delta oceuts i (1.205) because we assume thatthe os were chosen 10 he orthogonal] Fora nontrivial solution of (1.208), the Coffcientdetenminant vanishes det (Ha Eb u)=0 20) “This secular equation isan algebraic equation of degsee m with n roots Ef) B00 thal give them Gesvorder energy conection. Substitution of ‘exch incur into (1.205 allows one to solve Tor the st of events 6 (=...) tha g0 with the root-£}®. Having found the m-corect ‘erth-order wave fuetions 9! (=, ym) we ean then proceed to find £2, 4, and s0 on; the formulas for these corrections turn out to be cSsentlly the same as for the nondegenerate ease, provided that 0 i teed in place of yO i" When the secular determinant in (1.207) i in diagonal form (all of siagonal elements equal to zez0). it follows that the intially chosen unperturbed wave functions of the degenerate level ste the correct zeroth-order wave functions g!. Conversely, ifthe intl chosen np Turbed wave functions are the correct zeroth-order Tanetons, then The secular determinant wil Bein diagonal form, When the secular determinant in Block-disgonal form, the secular equation (1207) splits up into several equations. For example, i we have 4 fivefold degenerate unperturbed level and the scsla determinant hap pens 0 consist of a 22 Block and a 3%3 block fas in (19), then the Secular equation splits into two separate equations: moreover two of the” enn Mechanic md ern Sree correct zeroth-order wave functions are ineat combinations of 6 and v2 “had the other three eoreet zeroth-order functions are linear com rons of 49. $2 and 4" only “One met to pu the secular determinant in Block-diagonal form (and thereby simplify the calculation) i t© choose the inital zeroth-onder onctigos pt to be eigenfunctions of some operator 4 that commutes with both 8 and A Sine [11-40 i follows from (1.S1 that the integrals We vanish when J and Jf correspond to different eigensales of Therctore the secular determinant wil be in bock-disponal form, with ach Block coresponing (© a different eigenvalue of d THE CENTRALFORCE PROBLEM For a one-particle eental-foree problem, the potential energy is a function only of the particle's distance from the origin; V= V4); fom (1186), the Hamionian i fia myo/aP 427 9/0)+(LPMVE VE) (1208) Becavse ¥ depends only on r one finds that this Hamiltonian commutes wih the orbial angularmomentam operators 2? and 1. Hence the ineatunctios ¢of Fl ean aso be chosen as eigenfunctions of (and Z (1.20) 1041.2, (1210) Egemby, m= booth (iat “The eigenfunctions of £? and £, are the spherical harmonics Y¥P(@.9) these eigenfunctions can be multiplied by an abirary function of and il be eigenfunctions of Land L, (which do not involve 1), Heace for a has the form y= RIOD) (21) cenira-force problem, Use of (1.212), (1.208), and (1.210) in (1208) gives as the diterentat ‘equation satisfied by the radial function RO) CR mR) +2/ ARLE D2 VCORE) = ERC, (1213) Consider a two-paticl system withthe particles having masses my and im, and coordinates (4.23) and (439%) We define the Pla (OF Internal) coordinates => of the system by ce (1214) “The coordinates X,Y,Z of the center of mass of the system are given by at amin p_ martes (12s) ‘We shall impose the restriction thatthe potential energy V depends only fom the eelative coordinates ofthe particles: V= V( xy). Substitution of (1.218) and (1215) nto the kinetic-energy expression leas tothe Following expression forthe elassicalmechanical Hamutonan Hai +[ ph 2H+ Vicy.2)) (1216) hese Fis the total mass (MF Fm) the rede mase ps defined as ummm) ai) and the Hinear momenta py and p, have components defined by De=M(AX/di), py M(AY/dN, p= M(az/ae) Hdd), p= nC /e), p= det) Since the Hamiltonian (1216) ithe sum of «part dependent only onthe centeromass counts X,Y-2 and pat the Backeted fers) de pendent only om the internal coordinates ye, separation of vanes lows uso coalade shat he (complet) wave func the product of function Yugi X¥.2) anda Tuncion Yatra) Since Pey/2M a tren Tanta Yo ep we anton The oe tion am egeuncton ofthe operator corresponding to the bracketed terms in (L216) The energy the sum of sm energy of animal ‘motion ofthe ene tem of mass Man an energy of internal late) moti feo ps, We ve thet wave ons veri by seling up one-particle Schdinger equation using Seduced mass and the elative coordinates yz eso Ques Mesh ad rn tree {a3 THE TWO-PARTICLE RIGID ROTOR “The wp ig orr const of masses mam ae 10 he Caen oo ent Since the pais ae bel a ca ech ote, the potential enrzy does ot change a he feed distance ce and Pa constant which we may take J meee crea etry Kine VD a apc ease of V Bo the ative enone ofthe partes, 50 we may Se penn a TD to eparte the (arabonal and interns) oh so ee eh sm of tranatonal energy of the system and ti et motion, (ordinal the ery of ternal mason of ey of wo pe wbraonal a rational 1h worpaticle ot id itance be! fined, 0 there & only rotational cate th tar pd the intra wavefunctions and ener, we ineraal motion) Tunes of the Haraitoian coresponding (0 the aa gra) The potential ently =O 8 pecal ease of & bracketed et iim Lt, so we use spheral polar coordinates to desl cen force, St ft However, nce the interparticle Stance is eth the ere spheial por coorinate Fis wot a vara the ca ee tral angi cordinstes ad phic define only varias fe ar iterpartcle ais with respect fo 8 coordina ta tes wt he rfr bu tht des 20 lat), The eral ‘peer that tras eof Band gba, since this # cenraorce wa are nan tea eheral harmon YP.) The Hanon ae EMher dnvatnes omit (nce not a variable) wih i ‘Aygoee ecu toy ih m replaced by the reduced Ean oe end ve Vepeo. has te Sener ton Hy TAY Sn ors ternal mation is (12nd i29°(0.9)= EX(89) Use of (16D ses pale apd, 10.12, (2) is conventional to use J and M rather than ! and , fOr the rotational amguscinomentom qantam numbers Abo, the moment of iar of aaa pout am ax passing through the center of mass and perpen the for at aterpatte line is found {0 equal ad. (The moment of dicular vo Te en of paris about an ans is defined by J=E ine ote perpendiclr distance fom parce 10 the axis) Hence we easuenne/2, 1-012, (20) 144 Te nope Ao a The tworpartile rotor levels are (24+ Ibfold degenerate, since For each J thete are2/+1 posible valve of the quantum number “Tio tJ) and Es ndependet of Menno 1.14 THE HYDROGEN ATOM. The hydrogenlike atom consists of «nucleus of charge Ze and one lesion, (Z= Hor, = 2 for He? ete) The pot een (2 Het) The potential energy seven By Zehr (x) wher ri the dite ofthe letton fom the nce (om the nucleus. Since ¥ depends Sin teen cowbnt of he arcs the coy the sn af tramlatinal energy of the stom a whole a energy of ternal mots {Serton 12), The Hamtooin fr fternal motion 8 " B= (8/2 2eJe (im) ht the reed ma ation (121) ad and sate ‘Sones Te Hmfonan (Sa es cnt ee pron ene ’ Morre.9) (1m) where the radial function # i found by solving (1.213) with V= = Ze?/, Using a poerser ston on i ha te Hands (0 Rds Web 23!(22r/ma) (23) whore Nis the normalization constant, ais defined as oak it (.) ‘risa quantum number such that meh iene (25) snd Ls! van asaiated Lager polyomis, wh 1 nomial, woe highest power of + is n—1~ |, and whose explicit form we mercifully omit. " The bound-state enengy levels are found to be B= -(Z/\ E20) (1.26)® enum Mesa nd Er Ste since eyes on nym sae wi esa nat eret Form have these ener ‘Timer mule motion appronmated by fhe eto MASS were Boe ras). mee = 1 /me?=0.52918 A am peste, ten the reed mas St theta enced sate wave futons and energie, tere te a een all postive ceri at allowed eoriter code ix used co specify the value of the quantuin, number f: the A eer code ee ate Feaues Of LEIA GT Bn eet Theo - le the state with n= ‘ios 2p. 2B1~ Dida spect, Te nots a cle amt and n=? byron ‘wave functions are Nya) srg peat 0-2e rade?" Piaminge® (1228) 2 apne NZ/0" re apgne WME 2ah re PPC pte fare sinde 17 factor amakes the spheial harmonics comple, or Toe ao er fentons tat are sh getunctns of # and L Bm ta combinations ot i and Inl-m> For exam, 2 pany zsayaen (1229) ap, 22 70n. 420) app 129,29 eH UE /ah ve 2 (129) cebere (178) and (L113) wee awed Te ation 2, i Hed fF 2p Sse Spas the v coordinate asa f3etor: 20,=2Fe as sen hr momentum L (which aes from motion to obit antl ba a ain tay pales possess a ins (Opin an through space), elementary pa as 0 . ‘momentum. The spin S has no classical analog ad i elatvsic eer. The Schrodinger equation sa nonrelativistic equation, and in nonelt visbie quantum mechanics, the existence of spin must be introduced 48 Udhignal postulate. Analogous to the orbital angularsnomentyen pete tors Le Le La, we have spin angulat-momentum operator 8. SS which are hypothesized to obey the same commutation relations 4s For ‘orbital angula momentum: [s.3]-as,. [8.8 ini. [SS Jens, am) “The operator forthe square of the magnitude ofthe spin ang tum S24 $2482, We find [8.5,]- [525 ]=[8.5]-0 (2m) “The square of the magnitude of the spin |S? ofa particle equals store (1233) where the spin quantum number s ean be integral or half-intgral. The value of s i characteristic of the particle. Some values of + ate the following: electron, 4: proton, 4: neutron $: prmeson 0, The component ‘of S along the = aris has the possible values mh mens st het he (1.238) The quantum numbers + and m, ae the analogs of the orbital angular rmomentam quantum numbers and m. Foran deco, s=4, an m, can be — 4 or +4. We call the electron ‘pin eigenfonctons corresponding to thse two eigenvalues and Sactta, Siena ons) Also, since [5%.,]=0, we have from (1.239 Sante, Spm ane (1236) Its convenient to consider the quantum aumber m, as the variable inthe sin functions a and B: «= a(m) and f= jim), Since m, takes on only two values, rather than a continuous range of values, we use sums rather ‘than integrals expres the orthonormalty ofa and and the Hermitian“ uate Mesh wn Pe Scar property ofS, and other spin operators ¥ saimppare SF locmir 133) SF atmyptmny=0 (12%) TPim): elm) = Saton)[ $flm)]* (1.239) lint integral over the ful ange ofthe ‘ver the spin variables. ids sands for the symbol jr wil dente a d coordinates ofthe system including a summation ‘hos for one-electron, thre-dimensionl 9st, 2 ff awe “he symbol fo wt dene integration over he fal ange of he ps ‘sin variables Coordinates only, without summation over 5p Sra ta (16), the eletron-spin raising and lowering operators =sr5. 8 (1200) 4 of Section 1.7, we Analogous «othe equations Mf, Yoma™ have S pao (sr operator, we must have S, flea, where ‘oss e We cam evaluate by use af he ogmalzation of the sin sore com NE feitan propery ofS, and, one finds (Problem Ty icze: Choosing he phase of ea 0, we ave ‘so, since §, isa raising pane (12) (ne finds smi that Sanne (28) From (1.240) (1.248), we get Sya=snp, Sp the (i244) 146 The Pat Pe * Sa-tinp, Sm tha (1245) 5st a6 orbital angular momentum I. gives rise to a magnetic dipole moment, spin angular momentum 8 gives rise to a spin magnetic dipole ‘moment py. Dirac’ relativistic theory ofthe eeetom showed that y= (e/me)S= ~ 56/2) (1246) hese gi the electron factor. Although Dirae’s treatment gave & =2, subsequent more refined theoretical work and experimental dts show that i no exaely 25 eater &=2(Lba/tet--) 20023 (2) whete the fnestactre constant ais defined as 2 [he=1/137.036 (1248) ‘The dots in (1.247) indicat smaller terms involving a2, a, and 50 on 16 THE PAUL PRINCIPLE Comider stem of parties with sate Fnetion Wayne sa). whereg sts forthe four cordate hee spatial an on i) ci parce Sippose we nechange the coordina of panes osu Ye 4 ithe parce ofthe sytem se Meta them exper eeence felt qsntum ld thoy show thatthe se fant nest terete in form soa be yamesré wth pet acne he aries hve intel spn (40 or For 3 or) orange th rept 10 exchange the pares have baling per Ge oe fn). Thee the Pal picpie Inthe nonstate gustan case eat te Pl pce a aon! posite y “mt ‘ih espe! to exchange” we mesn tat ¥ unchanged on neon ‘the coordinates of identical particles: “ a Ho, a) BAe By “anisymmetrie wth respect vo exchange,” we mean that interchange of the coordinates of wentcal particles multiples ¥ by 1 Pa eo PMG dete)“ qe Mant smmeric wave ie sessing ane in a regi ant Parley avn lt ec hing egal pi an ou viene inc a ell Eso Fac ee hs tt ogaon, we et Y= 50 tht See sey aeons 20d Ma Ma HO then 9 te ety fr to io wth the same sin Mere sme nm pce The Pal rie a ke pnts at rom eho mes ent Ae cna ommractng patie | and 2. oe ncn alone Serie eaten SI ses ete pl rt othe sens ave in Sta te anche abrevate to ADE) The func: fr ete in fe spares tad 2 ae fant (ei eet) and ft) ae each Ries emetic ental a eo cng To lth al rice, at wy ne mata pt po wae ia ns nomabed inet contin 2-H ,()e@)+ 80/021 (120) 2 P[(e2)~s0)/2)1 (120) {or coune, if fand ae the same fntions, then (1230) vases and Ss repeal /V2)) oe i tia (10) and (1250 must be male by + sin ieee ree Get the fllowing fou pose woleton caret tee symmetric and one antsyamet: sooM aa) tor asp smmewie: 2 "Fa(np@y+Aqva@] (4282) 62) to-1 (2s) anigmmeric: (2-"{a()6Q)-AUDae@y}— @ 0 (1354) ‘The quay mughesIsted are forthe sgeslues of the ttn aaeean grag where the Lota spi Sis defined as S= 8, +8, Since are Te the symmea testo pat function (1.20) se seca wy the ansymets spin fenton (1.28) o ve ah rans et ficcign tat bs anuymmetic: te amisynmetne spatal anaes pn muiped by on of he symmette Sp eens (1251-125, 17 Mat « ‘An example isthe perturbation treatment ofthe He atom in which we neglect the iteeleeionic repulsion e?/ry, The correct zeroth-order wave funtion forthe ground state x I(t Ma(1)RA)~(Ya(2V}/2°2 (1255) where 1s denotes a hydrogenlike ombital. The coreet zeroth-order fune- ‘ons forthe states aring from the Is2s configuration are $8.2 P[ts(1724(2)+29(1)1s)2-MFa)B2)—_BCA)a(2)] 8; 2 ts(t7st2)—2(DLeQ)JaNaQ2 2s: 2's (122) —2s(1)15 EP *ALa(1YBA)+ ACN)ACL 45:2 Ls(ap2s2)—2aUI)L@)LAC AE) (1.286) The erm symbols ' and are defined inthe next section. For the states of the 152p configuration, we get zerothorder wave Tunctions similar 40 those of (1256), except that there are 12 (=4%3) zeroth-order functions instead of 4 the factor 3 aries from the spatilly degenerate 2). 2p. and 2p, orbitals. For three or more electrons, the wave function cannot be factored into & simple product of space part and a spin part see the ext seein, 117 MANY-ELECTRON ATOMS ‘With internal nuclear motion neglected, the Hamillonian for & many: ecto atom with atomic number BrP eL TTS. aan a The first term on the ight is the operator for the electrons’ kinetic enerey: the second term is the operator Tor the potential energy of atretion between the electrons and the nucleus (, being the dstance between electron i and the nucleus; the thied term fs potential eneray of repulsion between all puis of electrons (1 being the distance between cectons and J): the last tem isthe spin-orbit interaction (dncunsed. below). Te Audition, thee are other relativistic term besides spin-orbit interaction, which we neglect 1 we neglect interelectroniccepulsions and spin-orbit interaction, then« Quine Mechanar Str the atomie Hamiltonian s approximated by 7°, where = S( £u-2) (1258) Since f° isthe sum of hydrogenlike Hamiltonians, the zerotvorder wave function isthe product of hydrogelike functions, one fr each electron. ‘We call any one-electron spatial wave funtion an orbit, To allow for ‘ctton sit each spatial orbital mulled by a spin function either a orf) to Bie a pimorbial, To intgodce the required amisymmetry into the wave function, we take the zero-order wave funtion as a Slater deter! of spinorbitals. For example, for the Li ground state, the tormalized zerotharder wavefunction Le(a(1) ICC) 2s(aC1) 4} psjata) 14(2)82) 2s@)at2)} (1.259) 1:Q)aQ)_150)8Q)_ 25@)a0) Since interchange ofthe sows of « determinant matics it by ~ 1 (1.259) iE uatsymmetne. To Tully specify the Slater determinant, i suffices (0 imply lst the spin-orbtals; hence we abbreviate (1.259) to [Ioa1s/2s ‘Adopting. the convention that a bar indicates spin function and the ‘aches ofa ar indicates spin fonction a, we further abbreviate (1259) 19 hsts2s1 (126) [Note that i the spin-orbita in column duce of (1.25% were the same as that of ether column one oF column two, the determinant would vanish (Gince two columns would be wena), Hence antsymmetry of ¢ means {hat no two electrons can occupy the same spin-orbit in an approximate traveTunetion in which electrons are asigned to orbitals. ‘Voc of ms the approximation tothe Hamiltonian gives rise to electron configurations in which the electrons are ssigned (© orbitals. Thus for rouratstte Li we have the configuration 1°25, with two elctons inthe Trrorbhal and oe in the 2s orbital, The ground-state C configuration is 229g! Orbits having the same mand the same fare said to belong (0 {he same subshell the electron configuration i specified by stating how ‘many electrons ae a each subse Tn general, a given electron configuration has several wave function, cach coneaponding 10 the same eigenvalue of the zeroth-order Ham itonian 1°, This degeneray is partly removed by inclusion ofthe electron 17 Mayan At 5 sepulbion term Hage fig DDE (1261) thers spiting cach conigurtion int several ems (ae elo). Beane Oto the person ool agar moment aa let i> nok commute with the stom Hamiltonian, Delning tet ‘electronic orbital angular momentum L by. * " Led, (28) ‘one finds that the wa orbital anglar momentum operators Z? and ommote wih the Hanilionsan H+ Hy Salar to (1262) one deine the ul eecvonse spin anglar momenidm Sof the atom by S=.8, ‘Since we are infersed i he otal angular momenta, we need the rl {oration of angular momenta. Let My and M, be wo angular momenta ‘any ype (oth vbita oth spn, or One pin and one ori). Lethe sigenvales of 8. Myo ME. Myr be Uc mite aes DH mh respectively. Defining the ol angular momenta Mas M=M+M, (1263) ne tins hat he compere yy of St bey the walang ‘momentum commutation relations: hehe by the arguments of Section 17 the eigenvalues of Mand Af a6 ™ Seton JER FOI and MRM, J (1268) One can show tha the oa angsliemomentm quantum number Jt ‘on the possible values “ werd kes Jrictled thy bood\d (1268) (or example, it jy=2 a j.=3, then J has the posible values 5432. P as the possible values 54.3,21) The cienalut of the toast angulatsmomentum operas E> and Sf the atom are " sean Meri, Lata, (1206) S(S+DR, S041, 126) (One finds that states of a given eletronie configuration that have the sme ‘ales of L and S have the stme energy eigenvalue forthe Hamiltonian 11% Hg’ such ates ce sad 0 belong to the same frm. Dilleten ters* men ek Dc Se ing tom the same clectonic configuration have diferent neg, For ca ine Lape connguration, Weave syst fr te aa ac om (1248), we have S= 1, for he ttl estrone oe emer We have fn =i for ihe estons, amd (125) 2: Ty, Os Spy Sy, a 50 on The group ‘ly consists of the symmetty “operations of regulat tetrahedron, CH belongs to 34: its aymnety element are four Coes {one along each CH bond), three S, axes which areal Cy axes (ench biseetng two of the HCH bond anges), and six symmetry planes (each containing two C—H bonds). 6, isthe group of symmetry operations of & regular octahedron or of a cube. (The cube and the sepulee sotahedron have the same symmety clements) The octahedral molecule SF, belongs to ®a: 44 is the group of symmetry operations of a regular pentagonal dodecahedron of sosthedon, ty 8 the group of symmetry operstane of a sphete The yroups 5, Jy, 0, and $ are related lo Se, cou fn bea are chemically unimporant and will not be disease ‘A linear molecule belongs to ©, Dey ithe a center of symmetry Tex the symmetry operation & bring the point at (,).2) 0 (cys ATIC has mo center of symmety, oF to Rasy.) (1.20) Corresponding to the symmet space), we define the opeetor ‘operation & (which acts on points in ay which ae 08 Functions as follows Ofer. Mhay.2) (any The fncion yh the sme vale at point (x 2) a8 Shas at For example, C2) rotates poins by 90° counterelockuise around the ‘in the operator cy applied to «2p, oral changes ito a2 orb