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    5 views9 pages

    HF ParYan

    Uploaded by

    Israel Ribeiro

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    © All Rights Reserved
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    DENSITY-FUNCTIONAL THEORY OF ATOMS AND MOLECULES ROBERT G. PARR and WEITAO YANG Lunversiy of Nort Carta OXFORD UNIVERSITY PRESS « NEW YORK 1.1 The Sebdiger equation “The principles of densiy- functional theory are conveniny expounded by making relerence to conventional wave fonction theory. Therefore, {his fist chapter eviews clemenary quantum theory (Levine. 1K Meracher 1970, Parr 196, MeWeeny and Sutife 1989, Sabo and ‘Ostund 198). The ext chapter summarizes the more mivanced tech ‘sigs that we shall ned, manly having todo with deity maces, ‘Any protiem in the secre strcure of mater covered by uation including the tme, tn mat ese, however one stoma and molecules without time-dependent inter ay mhere E is the electronic enespy, W=W(.45-.. 3) it the wave Fonction, and is the Hamitonian operator, aS cameSare$! ars oe) -32 ata) ‘the “external” potential acing o electron the potential duc to mace ‘of carps Z,. The coordinates of elton feompisespuce ordinates and spin coordinates, Alomic ante are employed here and Through this book (unless otherwise specie): the length ni I the Bobr rau a(-0 5292 A), the charge unt the charge of hese, andthe mass unt he mane ofthe electron, my Wht addons fads are present, of eouse, (113) contains eta ters "We may wit (1.12) more compactly at Anti 40, ay where 5 ws ee tn, ts ws teense ect cy pid en$t wan the clecron-clecton repo enrzy operator. The total energy Wi the electronic energy pts the maleus-moceus repubon every ten 32% a That is, “ss woe aw 1s immaterial wheter one soles (1.1.1) for Eand ad Vox aera, fr incdes eit detiion fH apd works with the Seocges quntion inthe form AW = WW. uation (111) mast be saved subject 19 appropriate hound conditions, ¥ mont be wellbchaved creryhe, i partcult Joan to" aero a infinity foram tom or molecule er obeying appropriate Perioie Boundary condone for a replat inne wok. WI a Probably dstibuon functions the Seve tht 102) ar" = pod of ding the sytem, ‘ith postion coranates between ® and 2 GE and spin coors auto” a9) Here de = ay ded stand oe thes ft -o ost and Stands foe the Sets s30"- 7s, The sail coordinates ate como, Uae the spin soorinatcs ae dicrete Became elesrom ate fermions, ‘Walcot be. antisymmetric with rexpeet to inerchange of the oortates (both pace and spn of any two cleo. “There ave many sepa independent solutions of (11) or a given system: the egentancions Wa. wih corresponding energy eigemvales E., The st V, is complete, and the W, may always be taken 10 be ‘ribgonal and morale fs acordance with (1 10], Jveaet = (1) =o We denote the ground-state wave function and energy by Wand ‘ere fe mam intgrton over 3V spatial coon and summation over N spin corns Expectation vals of observables are given by formulas of he ype Jerawer onary wey w= 11 Jove he A ein rt stig cnet sige (pat manometer (Geemaluc ofA For example, i i normalized, expectation values of hee and poten energies ae given y the formals vi=(t)=fwrtwas aaty veel ()= frre an cay ‘eure te re et deers Tan; wy Pad feo es pense 12 Vaan pce rhe ond sate ‘When sytem tin the sate WF, which may or may no sity (1.1), {he average of many measurements of the energy ven by the formal naw) erm = SPA aa wre cay faves ay ‘Since, furthermore, cach prtclar measurement of he ener) ges One| ‘tthe eigenvalues off, we mmesitly have FIVI> (23) ‘The energy computed fom a guessed W isan upper bound to the tue tHoundsate coor Ey ll mumation of te tances [7] wih ‘spect toall alowed Aclcron wave funciom wil gv the toe ground nd energy Ela = Ee: ta een EN 029) mal pat of the inimeenerey pile of (123) goes mt folows apund in ems of the srmatand eget of, a25) “Then the energy becomes TiGres 029 FIGr een where Bis the eneray for the Ath eignsate of A. Note thatthe Urthogomlty of the Ws hasbeen sed. Because By 6, = Ey "ETW] 4 always greater than or equal 10 Ey. and i recherit ‘minimum £5 and only = Ga ‘Every eigenstate Wf am cxtemam of the functional EW) tn hee words, one may replace the Schrdnger equation (1:1) wih the “ariaiona pencpe ° a2 ‘When (1.2.7) i sted, (11.1), and ce ver Tis convenient esate (1.2.7) ma ay tht garnet he sea wil somata be Sorat. Tis can te dc he meted {Sf taprane ndctermined magn (7 of Arn 108 pes SrA} Exscmiaton 0 (91 N)sbje oe otra C8] We ‘egufvlem to making tatonry the quanity (HH) EQ) ‘ethot constant the Lagrange maliper This per UIA IW) ~ECW IW] =0. ‘One must solve his equation for W sa function of then ‘normalization is achieved It elementary t0 show the. euetal ‘uraence of (1.28) and (I-11). Soliton of (12.8) with forme of ‘sted to approniate forms W of agen type (tt aba of all ‘Mlowable W) wil pve welldefined text approximations | fovrect W, and Ey. By (123), Eym By and $0 convergence of the ncgy, fom ove, i sured sone anes more and move fede ‘Most contemporary cations on elect tute redone with this ‘ariatonalproedar, in some linear algebra implementation "Excted-tate eigenfunctions apd eigenvalue aso sat) (128), but te correspening methods for determing approximate, and Ey encounter onbogoeaiy dice. For exampc, given , Ere mo ‘ecestaiy above Euless Wy orthogonal 1 the exact Vy "To summarize: Fors system of W cetrons and given maear potenti (eh, (128) dens a procedure for going from Nando) to the roundsiale wane function Wand hence through (11.12) 0 the Efountateeneriy EIN of and oter proprio teen. Not tha the aatement there ie no mention of the Linte-energy of election fepubion part of fl, becuse these ate universal in tat they ae Atermined ty N- We ay thet Eis functional of Wand (0) 13 The Hartee-Fock approximation Suppose now that sapproximated us an antsymmetzed product of N ftonormal spin orale (x), each product of spatial ral $8) {a pin funtion of) at) ox Ps), the Sater determinant sts) wae => wate) Wane ct | PE) WHO) wate) ee) wa) va) Fattinned aay “The Harree-Fock approximation (Roctaan 1951 the method where by the orthonormal otal y ae found that misimee (12.1) for thi Serial form of. “The normalization integral (yy | Pr) 8 equ 01, and he eneray expectation value found tobe ven bythe Hema (oe example ee Par 1963) a= (tality =Snei Sony 0a afer efferent vieawarenen — ase 1-105 + vans) de 033) Ka[Jvteoneo! wcawitrinte — 038 ‘These itorals are all veal and J, Ky 20. The Jy ae call Cowlomd ‘repay the K, ae called exchenge imepral. We have the portant sa * dn Ke (36) ‘Tiss the reason the double summation in (1.32) can Inde the = Minimisation of (1.32) subject to the cethonormalcaton conditions ic ow ges the Hatoe-Fock diferent equations Wiad de 8, aan Foi 2 even) a38) a fasieaess as) it te Cnty opt x) hy paw cay te waa S Joteomao yards — can a favao=S foreareo2nere — cam sith (4) an asbirry function. The mates € consis of Lagrange ‘ule in general comple) stained with the contrite of (13.7) bo, a4 as) 0 that eis Hermitian (Roothan 1951), ‘Matipying (13.8) by yf and interating one obtains the formal for orbital energies am (WF IW sku-m caso sig ean gig st 1:32, fw Sonte ass tec te sub Vm fr he tl scorn pn =e 3 vex [vier 3) ae" Sonn si) Fer es al eer cena chang mle mpohicnions ha from (1.9) Wow Se Wet Woo asim SH Va Vo sis) [Note that neither Fy 08 iy equal 1 the sum of obtener. ‘Stun of (138) max proceed erative since the otal tat solve he problem appear inthe operator F Consequently. the Hareee- Fock method isa nonlinear “settconsisten eld” metho. ora system having an even tombe of electrons a what i called the rested Hanee-Foek mahed (RUF), the N avtas 9 ate taken 10 Comprise N/2 orbitals of form gu(shats) and N/2 ott of form ‘GHB. The energy formula (1.23) becomes caw) were = | 9200I-IP + weet de aaa dea[fiesoarinoaeindy aay kex[Jotmviwmoeterinds (322) se Hae Fok uot (1. od Postey= eubhe) (1.3.23) ‘wth the operator F given by (139) ané (13.10), with (13.11) and 13.12) replaced by invtsy=2 ¥ fieaey’Lensiey 4329 kaiyere S [ocerer Lens “The determinant wave function 1.3.1) for this “osha ase asa lc Pledas) oAedBla) ——- grated 1 | outedaes) eC) -- Oyate)B6 Yorn | . ‘ Adela) AsledPle) Pantera) 1.826) ‘An important propery of this wave function [and sho of the more fener (131) that unitary transformation Of the oped ta ‘(or ) 10 another set of orbitals nq leaves the wave fection Srchanged. excep posily by sn incomequental phase factor The fperatrs fant Po (1.3.2) tough (13.25) for of (13.9) trough CTS) ave ake lavaant to nich » tanormation (Roothton 195 Szabo and Oshnd 1982, page 10), Tha ist sy we et nea ZUame az ee Ui nary mat, then (1.28) becomes wus 328) Pn Seton, 32) o e=uu" 330) ‘This exits the considerable freedom that exist inthe shoe of the ‘Sine the mati € is Hermian, one may choose the mati U to dagonaize it The corresponding orbits, called the canonical aree-Fock orbit, sats the canonical Haree“Fock equations, Pale) e360) asa) Equation (1.3.31) i comiderabty more convenient for eulaion than (1323). Furthermore, the ofits that ate solutions Of (1331) ae ‘owest-energ)snge-determinamtal descnpion tor the on ‘niaot tail fom the canonical Hartree Fock orbitals of (1.3.31). One then fos, approxima, aan asm here fa the ionisation energy ascited with removal of an eleciton fom «he orbital ATs equation i in error, teense i ignores ath ‘reorganization and ero inthe Haree-Fock description (led corel thom energy: se the ment selon: fortunately thes tend 0 ane "The orbital energies forthe canonical Hartree-Fock orbs abo ‘contol the longrange Behavior of the exis Nivel, one woud apet frm the ne letonnatee Of (13.31), ng exp (e202) ] for trge rs Ths i correct for atoms wth + eleons ony, bt nti ‘Peal Insed, in goveal the reson (least-gative) o€ all of te ‘Serpe, determines the lonrange behavior of lf of the onal: Ae~empl-(-2eed" forlager (13.35) ‘The long-range properties ofthe exchange pat of Pate response for (his temarable beluvior (Handy, Marto, and Siverstone 1969) The bperstor Fit nora Sterm-Lowile operate "or the cosedsel case entre!) equtalent othe canonical Hartee- Fook description ae the cela Harec-Fock description sind the loclied Hartree-Fock desription. Clean! Harree-Fock obs (Parr and Chen 1981, Nyden and Parr 1963) are obits the able tars of which aes coe to each other a posi in sein sense foe them the mae eof (13.29) cralnt matrix (agonal slement iM equal, every row a eye permutation of every et) Located Hestce-Fock orbits (ESniton and Racdenerg 1963) ae exis with maximum selrepolson or minimum itrorbial exchange fatrscton ‘Te clecton pasion pat of (1.5.19) fom (138), Wend-K aay tere soZau-Zmo[ZneZu] — aay keZaeZur[Ze] aay 4 are cach invariant to unitary transformation, bot the terms in Squte brackets in these equations a nt the uatry tentormation fo ‘oelizd ott an thereon he effected by maiming Moet SB hu= Kee) assy oF equivalently, by minimizing Dk CCculant oils are inortat because they ae orbitals that have cquileat mathematical and pha footing, each very sow to the square root ofthe elton demity pet particle. Localized orbital ae Imporaat beease the eabtence econcles molecalarxttal theory ‘sts the more tadtional descriptions of meecues mr had together Oy Tread chemical bond trom the beponing one eglcts all introbital exchange term in the Hartee-Fock method, which corresponds 10 aung 1 product of ‘rita a the wae function i place of the antiaymmetrid product of (131 oF (1.330), one ges the omhogonalieed Hare mathod. The ‘ose equation (1.325) replaced by Aiet= Baal 336) where Av eerh ee) fav iray=[[wors2 3 vse] bem aan Joh me sk SE st om Sa Rees Sattar cea ots a a Son ie mae nian ann eromaer een nes sem i ed pa ae {Gis ke St eS pw oe a eae inate fees emotes ae Seah ioe See nae oan ae Sepa ra caren tal cl Soe ent Teeeeres imei grees een ee epee eainsen atte eae ao Seieecs pete igen hoe leer ae nee Gata Ste ti mate eres eee Stas ied te we acre eee ici od eons Caan tied aaa Seca ah ran awa ae oa or one carers mn encrae nae pear ees weoca ny Semana aatese ost we Seren cs i i Na eo moran rey Sg a Nae te RESO sSiy aparece et aa Set tae nae ae ee akan oan een tena bien ine coe (rms) matin sgeraae problema of high ‘Geemitn,n itch esac semen ae cated rm say of ‘Spee crated forth bas ncn. Ire cl heb coe 20, eo om we fom (12) what Se ncoeny nega il Be seefatonsos am 3.0) 3.4) a econ -elecon repuion imerals inimeff Sometimes these ae all compsted exactly n which cane oe sys tha ‘on han ab ino method (For reviews, te Schacter 1977 and ae) 197. The term "a iio” wat sed st though intended to hate 2 ferent mening. in Pat, Craig. and Rows 1980) Sometimes these ae ‘etermined by some recourse to experimental data, in wich au oe as Stomiompiral method (Par 18h, Sep 197). Sach dealt ae of ourse vital, but here they wl ot be Of much cooeeh 10 us Se he resent expontion tended tid dndn, 3a) 14 Comreation energy When one is interested ia higher accuracy. there are sesighforward ‘xtsions of the snle-determinantal dexrpton to simple “malcom quran” desipions nvlving fw determinants (lor example, Seton Sor Szabo and Oxtnd 192) ‘The craet wave fncin fora stem of many interacting lero is sever a single determinant cc's simple combustion of few deter. trinants, however. ‘The clclation of the eur in energy. called ‘Conlon energy, bete defied 10 be megane, Bi = E~ Ee aay) isa maor problem in many-body theory on which there has Been avast amount of work and) mich progtes tar been made, The methods employed facade the linear mixing of many determinants (nitions), faledcondguation interaction (Chapter 4 of Szabo ed Oxund 982), ‘nd many-body perturbation echniqus (Chapter of Sabo and Ostund 192), For comprehemave reviews, see Stanofia and Brace (970) rey (1976, tad Wilson (1982) Cortlation energy tenis to emai constant for stom ané molecular ‘tangs that conserve the numbers and typeof chemical fonds, Bu ‘an change drastically and become determinative when bonds change. Ie teriids can vary fom 29 or 30S erm of aories pr make, froma few hundred ofan stomic unt on up. Exchange ener ate a drier af map or mor per even he eexcngstrm 1S Neto density nan clacton system, the numberof electrons per unt volume i 3 {Bren sate is the eecron deny fo hat tate. Ts quant wil be of [eat importance im ths hook: we designate by pt) formal in {ems of 8 even ofa sina tate O80 ‘This is nonnegative simple function of three variables, x.y, and 2 integrating wo the total name of eects, Jor ée=w asa “There has been much attention paid to the eleton deny over the years (Smith and Absar 1977, Maps of electro deasies sre sate many places (for example, Baler 170) Foran som in pound ste the density deceases monotoncally away fom the nueus (Weinstein, Potter, and Srobrenik 1775) in approximately piecewise exponent fashion (Wang and Parr 1977), For molecules, tes siht demstues ook lke superposed some Jensen. on close iaspection (experiment oF theoretic, modest (bt sil quite small in absolute terms bale of ‘ensty are cea in bonding repons "At any atomic nucleus imam atom, moleele, or solid, the eletron ‘ensiy has» ite value; fr an atom we designate this 0) Inthe ‘eghovbod of «maces there alway a csp in the deny ving 10 the necessity for Hamitonian terme ~V~ (2y/r,) ao 0 case bomeps in fw thee. Te specie cusp condition (or example, see Daven ——— Sie) 1 hee 7) the sphere serge ofp.) "Another important rest the long fane law fo lecton dens p~expt-202ha) "1 ase here fan i the ext es ionization potemal (Mowe Par, and Levy Iss; eit paper ao contains a genealaation of Koopmans’ theorem), ‘The corresponding Hartree-Fock renk willbe, from (1-333), Pe €=9-20-2ea) ass) where ue EORIMAES lB (13.22) inal we record hee tan fsa about electro demity from the standard firstorde pererhation theory for 1 nondegenerate sate Seppove the state VF is perturbed tothe state Py W240) by the fone-lecron perturbation AV=, Av(e). The energy change to fist dere miafvearvta=[ninavnran, 050) dee ted hn bo et rr > a), i vee ZONED y, as ‘The clecton-demity change i then, tft orer in, aninv=n {fete rend ditt, ene ORAM ff wrap teat} Be een dn ase ‘here the “functional derivative” p70 f dined by i BA ence te foo weve te tn] & EB 39) ‘This quanity is ced the near ropome funtion. The symetty prconacd 21 (1.59) i importa Is portation of plat potest "Sen change a point 2, then the sae petutation at pt 2 wl ‘produce pot {precinct the same deny hangs Note at Bout -0 30) All ofthese formals assume thatthe number of elections sted. Fora [teal dacesion of functional derivatives, ce Appendix A 1.6 Hetimane-Feynman theorems and vial theorem tA be a parameter the Hamaitonian and (2) be an eigentuncton of fi Then 4e_cmaniaayy oa ao cwr¥) “eye HAM = BUI) ray ~ 6a = HA wan ™ — pay = [eelamiony, i raya) = [ORME gs) ‘These. identities are the_ diferent! Helmann-Feynman theorem Cormat), the mera HetimareFeyaman theorem (Loma), abd the Imegrated’ Weimann-Feynmanihorem (lrmala) (Epi, Hatley ‘yn and Pat 1967). The detvave 3A731 i wrens a part

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