量子化学简介1113.pptVIP

量子化学简介1

量子化学是用量子力学原理和方法研究分子微观结构以及与物质的物理和化学性质关系的一门边缘学科。在它过去多年的开展过程中，建立了一系列理论和计算方法，概括出许多对化学开展有重要意义的概念和规律。特别是七十年代以来，随着计算机技术的开展，量子化学已进入一个新的开展阶段，其研究成果使人们对物质结构与性质的内部联系以及化学现象本质与规律性的认识大大深化了。量子化学概述2

理论方法从头算分子轨道理论〔AbInitio

MolecularOrbitalTheory〕半经验的分子轨道理论〔Semi-EmpiricalMolecularOrbitalTheory〕密度泛函理论〔DensityFunctionalTheory)3

Schr?dingerequation: E?=H? 分子轨道理论4

Schr?dingerequation:kineticenergy(nuc.)kineticenergy(elect.)2kineticenergytermsplus3Coulombicenergyterms:(oneattractive,2repulsive)5

Schr?dingerequationafterBorn-OppenheimerApproximationkineticenergy(nuc.)kineticenergy(elect.)1kineticenergytermplus2Coulombicenergyterms:(oneattractive,1repulsive)plusaconstantfornuclei0constant6

Simplifyingassumptionsareemployedto‘solve’theSchr?dingerequationapproximately:Born-OppenheimerapproximationallowsseparatetreatmentofnucleiandelectronsHartree-Fockindependentelectronapproximationallowseachelectrontobeconsideredasbeingaffectedbythesum(field)ofallotherelectrons.LCAOApproximationBasisofM.O.Theory...7

Born-OppenheimerApprox.Statesthatelectronmotionisindependentofnuclearmotion,thustheenergiesofthetwoareuncoupledandcanbecalculatedseparately.Derivesfromthelargedifferenceinthemassofnucleiandelectrons,andtheassumptionthatthemotionofnucleicanbeignoredbecausetheymoveveryslowlycomparedtoelectrons Htota(Tn)+Te+Vne+Vn+VeKineticenergyPotentialenergy(Tnisomitted;thisignoresrelativisticeffects,yieldingtheelectronicSchr?dingerequation.)8

Assumesthateachelectronexperiencesalltheothersonlyasawhole(fieldofcharge)ratherthanindividualelectron-electroninteractions.IntroducesaFockoperatorF: F???????? whichisthesumofthekineticenergyofanelectron,apotentialthatoneelectronwouldexperienceforafixednucleus,andanaverageoftheeffec