激发态理论研究方法.pptVIP

Summary ?How to choose the method according to different systems 2……10…….20………50……..100……….. semiempirical CIS MCSCF TD-DFT, CCSD-LRT MRCI FCI Theoretical method for excited states Method classifications Wave Function Ab initio (MRCI,CIS…) Semiempirical(Zindo/1,INDO/S,CNDO/S…) DFT TDDFT, MC-DFT,DFT+CI… Ab initio method Separation of variables B-O Approximation Hartree-Fock Theory Molecular orbitals Electron correlation methods ?Configuration interaction Full CI: ?M?ller-Plesset Perturbation Theory Limited CI: *properties: well-defined, size-consistent, variational,very expensive and impractical for all but the very smallest systems CIS, CISD,CISDT, QCI, QCISD,QCISD(T) HF Limit Sch?dinger Equation Full CI … … … … … … … … … … … … HF MP2 MP3 MP4 QCISD(T) Electron Correlation→ Basis Set Type Minimal Split-valence Polarized Diffuse High ang. momentum … ∞ Density Functional Theory Current DFT methods partition the electronic energy into several terms: corresponds to the classical energy of the charge distribution accounts for the remaining terms in the energy *the exchange energy arising from the antisymmetry of the quantum mechanical wavefunction. *dynamic correlation in the motions of the individual electrons Ab initio methods for excited states ΔSCF methods Excitation energy in the HF/SCF model: ΔEorbital(ELUMO-EHOMO,etc.) What’s left? ?Electronic correlation energy ?Multiconfigurational description of the transitions Single-configuration methods: *CIS(CI-Singles) *Response methods: RPA,SOPPA *Coupled-cluster Methods: EOM-CCSD(T), CC3, SAC-CI Multi-configuration methods: *Multireference CI: MRCI, MR-SC2CI *Multireference perturbation: MR-PT (CASPT2,..) *Multireference Coupled-cluster: MRCC Single-reference methods: CI-Singles Reference: HF-SCF, yielding MOs Excited states: linear combination of singly- excited determinants App