Variational geminal-augmented multireference self-consistent field theory: two-electron systems. 2010

Sergey A Varganov, and Todd J Martínez
Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305, USA.

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.

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