资源描述：
《南京大学结构化学双语》由会员上传分享，免费在线阅读，更多相关内容在教育资源-天天文库。
1、Chapter7Transition-MetalComplexesTopics:AtomsandorbitalsinElectrostaticFieldGroupTheoreticalAnalysisOpticalSpectraandMagneticPropertiesStereochemistryMolecularOrbitalTreatment-BondingandCovalentComplexes17.1AtomsandOrbitalsinElectrostaticFieldTopics:SquareLigandFieldOctahedralField
2、2SquareLigandFieldporbitalsE0pzpx,py3SquareLigandFielddorbitalsE04OctahedralLigandFielddorbitalsE0D56TetrahedralLigandFielddorbitalsE0D77.2GroupTheoreticalAnalysisTopics:OrbitalsplittinginOctahedralFieldSplittingofTermsWeakFieldScheme（弱场方案）StrongFieldScheme（强场方案）8OrbitalSplittinginO
3、ctahedralFieldAtomicorbitalsinzerofield上述基函数集合皆为中心对称力场中的不可约表示基函数。但是，在八面体场中，可能会发生分裂。9CharacterTableOI8C36C2'6C43C2(C42)A111111A211-1-11E2-1002z2,x2-y2T130-11-1x,y,zT2301-1-1xy,yz,zx10由群表直接可知：s=>A1gp=>T1ud=>Eg+T2g如何判断七个f原子轨道,和F,G,H等谱项的分裂呢?11Atomicorbitalingeneral,Iftherotationsisabout
4、thez-axis,theonlychangesinthewavefunctionisin121314OhI8C36C2'6C43C2(C42)SplittingPatterns11111A1gp30-11-1T1ud5-11-11Eg+T2gf71-1-1-1A2u+T1u+T2ug90111A1g+Eg+T1g+T2g15OhTdD4hsA1gA1A1gpT1uT2A2u+EudEg+T2gE+T2A1g+B1g+B2g+EgfA2u+T1u+T2uA2+T1+T2A2u+B1u+B2u+2EugA1g+Eg+T1g+T2gA1+E+T1+T22A1g+A
5、2g+B1g+B2g+2Eg16SplittingofTermsWeakfieldandstrongfieldschemesWeakField:StrongField:Field–orbitalinteractionismuchweakerthanelectron-electroninteractionsintheatoms.ThefieldisconsideredtobeaperturbationtotheTERMsofthemanyelectronatomsField-Orbitalinteractionismuchstrongerthanelectron
6、-electroninteractions.Therefore,electron-electroninteractionsareconsideredasaperturbation.17WeakFieldSchemeStep1.DerivingtheTERMs.dnTERMsd1,d92Dd2,d83(F,P)1(G,D,S)d3,d74(F,P)2(H,G,F,D,P)2Dd4,d65D3(H,G,F,D,P)1(I,G,F,D,S)3(F,P)1(G,D,S)d56S4(G,D)2(I,G,F,D,S)4(F,P)2(H,G,F,D,P)2D18Step2.
7、ConsideringthetermsplittingS=A1P=T1D=E+T2F=A2+T1+T2G=A1+E+T1+T2…19GroundStateSplittingofd1,d2,d3Groundstates:d1,d2,d32D,3F,4F2Eg2T2g3A2g3T1g3T2g4A2g4T1g4T2gExample20Computationwillgivetheenergeticalpatterns:2D2Eg2T2gD0.6D0.4D3F3A2g3T1gD0.6D1.2D3T2g0.2D4F3A2g3T1gD0.4D1.2D3T2g0.6Dd1d2
8、d321GroundStateSpli
