Variational geminal-augmented multireference self-consistent field theory: two-electron systems

Sergey A Varganov; Todd J Martínez

doi:10.1063/1.3303203

Variational geminal-augmented multireference self-consistent field theory: two-electron systems

J Chem Phys. 2010 Feb 7;132(5):054103. doi: 10.1063/1.3303203.

Authors

Sergey A Varganov¹, Todd J Martínez

Affiliation

¹ Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305, USA.

PMID: 20136301
DOI: 10.1063/1.3303203

Abstract

We introduce a geminal-augmented multiconfigurational self-consistent field method for describing electron correlation effects. The approach is based on variational optimization of a MCSCF-type wave function augmented by a single geminal. This wave function is able to account for some dynamic correlation without explicit excitations to virtual molecular orbitals. Test calculations on two-electron systems demonstrate the ability of the proposed method to describe ionic and covalent electronic states in a balanced way, i.e., including the effects of both static and dynamic correlation simultaneously. Extension of the theory to larger systems will potentially provide an alternative to standard multireference methods.