Multiconfiguration optimized effective potential method for a density-functional treatment of static correlation

Data di pubblicazione: 14 Apr 2008

RivistaFonte dati: ARCHIVIO

An approach to treat static correlation within a density-functional framework is presented. To that end, a multiconfiguration optimized effective potential (MCOEP) method is derived. In contrast to standard multiconfiguration self-consistent field (MCSCF) methods and previous combinations of MCSCF procedures with density-functional theory, the MCOEP method yields well-defined physically meaningful orbital and eigenvalue spectra. In addition to the electronic ground state also excited electronic states can be described. The MCOEP method is implemented invoking the localized Hartree–Fock approximation, leading to a multiconfiguration localized Hartree–Fock approach. Applications of the new method to the dissociation of the hydrogen molecule and the isomerization of ethene and cyclobutadiene show that it is capable of describing situations that are characterized by strong static correlation

Editore
American Institute of Physics
Fonte
The Journal of chemical physics
ID archivio
81ae411fcc8b54885f5dd62bf2b6a8de
Riferimenti
Volume: 128 Issue: 14 Pages: 144109