LDA+U第一性原理方法.pptVIP

IntroductiontoLDA+Umethodandapplicationstotransition-metaloxides:

Importanceofon-siteCoulombinteractionU鄭弘泰國家理論中心(清華大學)28Aug,2003,東華大學

OutlineDFT,LDA(LDA,LSDA,GGA)InsufficienciesofLDAHowtoimproveLDASelf-interactioncorrection(SIC)LDA+UmethodApplicationsofLDA+Uonvarioustransition-metaloxidesConclusions

DensityFunctionalTheory(DFT)

Hohenberg-KohnTheorem,PR136(1964)B864Theground-stateenergyofasystemofidenticalspinlessfermionsisauniquefunctionaloftheparticledensity.Thisfunctionalattainsitsminimumvaluewithrespecttovariationoftheparticledensitysubjecttothenormalizationconditionwhenthedensityhasitscorrectvalues.

Localdensityapproximation(LDA)

Kohn-ShamschemePR140(1965)A1133

InsufficienciesofLDAPooreigenvalues,PRB23,5048(1981)LackofderivativediscontinuityatintegerN,PRL49,1691(1982)Gapstoosmallornogap,PRB44,943(1991)Spinandorbitalmomenttoosmall,PRB44,943(1991)Especiallyfortransitionmetaloxides

PRB23(1981)5048

PRL49(1982)1691

PRB44(1991)943

AttemptsonimprovingLDASelf-interactioncorrection(SIC)PRB23(1981)5048,PRL65(1990)1148Hartree-Fock(HF)method,PRB48(1993)5058GWapproximation(GWA),PRB46(1992)13051,PRL74(1995)3221LDA+HubbardU(LDA+U)method,PRB44(1991)943,PRB48(1993)16929

Localdensityapproximation(LDA)

Kohn-ShamschemePR140(1965)A1133

Self-interactioncorrection(SIC)PerdewandZunger,PRB23(1981)5048

BasicideaofLDA+UPRB44(1991)943,PRB48(1993)169Delocalizedsandpelectrons:LDALocalizeddorfelectrons:+U usingon-sited-dCoulombinteraction(Hubbard-liketerm) UΣi≠jninj insteadofaveragedCoulombenergy UN(N－1)/2

HubbardUforlocalizeddorbital:nnn+1n-1Ue

LDA+Uenergyfunctional:LDA+Upotential:

LDA+Ueigenvalue:Foroccupiedstateni=1,Forunccupiedstateni=0,

peEexact(H)=－1.0RyELDA(H)=－0.957Ry～Eexact(H)