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11.,hEhpνλ==2.,,,,xyzxphyphzphtEh∆∆≥∆∆≥∆∆≥∆∆≥1.1(,,,)xyztψ(,,)xyzψ*ψψψψ*ψψ*dψψτdτM.Bornψψψψ⋅=*22.211221122ˆˆˆ()AcccAcAψψψψ+=+**2121ˆˆ()d()dAAψψτψψτ=∫∫123.3AˆAψaψˆAaψψ=ψAaaˆAψˆA24.412,,,nψψψψ1122nniiiccccψψψψψ=+++=∑A**ˆddAAψψτψψτ=∫∫5.5PauliSchrödinger1.Schrödinger222d2dEmxψψ−==2()sin()nnxxllπψ=2228nnhEml=123453Schrödinger1.Hamilton21ˆ2ZHr=−∇−2.Schrödingern,l,m()(,)nlmnllmRrYψθφ=:0:1:n∞:0:1:1ln−::1:mll−ll2ˆ,,zHll2420222(),,81nZEllmnehµε=+−==zn3.1n−1nl−−l22()()DrrRr=()dDrr~drrr+()nl−spp,p,pxyz1.Hamilton2111ˆ22iiiijiijZHrr≠=−∇−+∑∑∑2.Hamilton1ijrSchrödingerSlater3.Slater411|2,2|3,3|3|4,4|4|4|5,5|sspspdspdfsp20σ=30.35σ=1s0.30σ=4sp0.85df1.0051.00σ=4.()2**213.6,,iiiiiijjZEZZnσσσ=−=−=∑1.1212:||:1:jjjjj−+SLSLJjjjJ2.21SL+21SJL+L012345SPDFGH3.Hund1S2SL3SLJJ4.21J+:(:1:)JmJJ−Jm50S∆=0,1L∆=±0'0LL=⎯⎯→=50,1J∆=±0'0JJ=⎯⎯→=0,1Jm∆=±0J∆=0'0JJmm=⎯⎯→=6ψˆH0E*0*ˆddHEEψψτψψτ=≥∫∫1.1122nncccψψψψ=+++12,,,nψψψ12,,,nccc2.LCAOMO1111121211212122222211220nnnnnnnnnnnnHSEHSEHSEHSEHSEHSEHSEHSEHSE−−−−−−=−−−##%#*ˆdijijHHψψτ=∫ij=αij≠β*dijijSψψτ=∫ij=1iiS=ij≠nn0ijS≠0ijS=3.z71zσ2,,zzspd2zπ,;,xxzyyzpdpd3zδ2222xyxyxyxydddd−−−−4.22ppπσ22ppσπ5.22O,B1.0122(1)8JhEJJIπ=+2Irµ=1212mmmmµ=+21J∆=±3J2(1)BJν=+2.011()0,1,2,2Ehυυνυ=+=21υ∆=±3.Raman4.-81.2.3.4.12nn345{,,,}GABC412EAAEEAA==3A1A−11AAAAE−−==4()()ABCABC=1.vC∞hD∞92.31n2CD3CA.nhCBnvCnC4DA.nhDBndDnD3.134TAhTBdσdTT243OhOO356IhII412hhiCCsCC==1.,,TOI2.10VSEPR1.=+±=H1OSN2.123452----3V---4V--5T6TV7sps,phD∞23CO,N−sp2s,px,py3hD33BF,SOsp3s,px,py,pzdT4CHdsp2sp2d22xyd−,s,px,py4hD24Ni(CN)−dsp3sp3d2zd,s,px,py,pz3hD5PFdsp3sp3d22xyd−,s,px,py,pz4vC5IFd2sp3sp3d22zd,22xyd−,s,px,py,pzhO6SF11HMOπσπππpziiHαijHβ0ijS1iiS=0()ijSij=≠12ikikkncρ=∑kiknkikcki2ijkikjkkPncc=∑3maxiijjFFP=−∑πnmπmπpnπ()HOMOLUMOHOMOLUMOσ122CLUMOLUMO13MLMLnMLML1.MM-2.ππ1.2.MLL5d∆PP∆P∆3.4.ML14MLσπM222xyzx-y:s,p,p,d,dσxyyzxz:d,d,dπ*ge2gt∆∆PP∆P∆σπ−πσxyyzxzd,d,d*πσπ−151.123FEVF+V=E+24:2.(1).(2).(3).3=+(1).16a2a3a4aTm=ma(m=0,1,(2).Tmn=ma+nb(m,n=0,1,(3).Tmnp=ma=nb+pc(m,n,p=0,1,4(1).aa=|a|,(2).ab2(3).abca=b=cabcPIFa=bcabbcab=120h17a=bcabcPIabcabcPIFca=b=c==120abc==90abc901abc21uvw,r,ra,b,c,r=ua+vb+wcuvw2[uvw],[uvw],u,v,w3[uvw]ua+vb+wc3(hkl)3x,y,z,3r,s,t(a,b,c)111rst::111rst::=h:k:l,(hkl),(hkl)4d(hkl)(hkl)2d(hkl)18:d(hkl)=ahkl()222++,(hkl)h,k,l,,,1.1,,,:CnCnnL(α)σσmMiiiISnSnnL(α)I,,,,,,n,n=1,2,3,4,6“”,:iI1mM21L(0°)2L(180°)3L(120°)3=I+33+m=64L(90°)6L(60°)194L(90°)I232,,:,,,(5,7,.....),,,,3232,32::,,:,,2.,,,1,:(t)(T),-(T)niL(2πn),T(ina)(n=1,2,3,4,6,i=1,2,...,n),,nini=L(2πn).T(ina)=1,2,3,4,5;i=1,2,3,...,n,:abc,abc12ab2120c21;n:a12a,b12b,1212ab+(121212abc++);d:1414ab±2230,,,230,230