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A size-consistent approach to strongly correlated...
Journal article

A size-consistent approach to strongly correlated systems using a generalized antisymmetrized product of nonorthogonal geminals

Abstract

Inspired by the wavefunction forms of exactly solvable algebraic Hamiltonians, we present several wavefunction ansatze. These wavefunction forms are exact for two-electron systems; they are size consistent; they include the (generalized) antisymmetrized geminal power, the antisymmetrized product of strongly orthogonal geminals, and a Slater determinant wavefunctions as special cases. The number of parameters in these wavefunctions grows only linearly with the size of the system. The parameters in the wavefunctions can be determined by projecting the Schrödinger equation against a test-set of Slater determinants; the resulting set of nonlinear equations is reminiscent of coupled-cluster theory, and can be solved with no greater than O (N5) scaling if all electrons are assumed to be paired, and with O (N6) scaling otherwise. Based on the analogy to coupled-cluster theory, methods for computing spectroscopic properties, molecular forces, and response properties are proposed.

Authors

Johnson PA; Ayers PW; Limacher PA; De Baerdemacker S; Van Neck D; Bultinck P

Journal

Computational and Theoretical Chemistry, Vol. 1003, , pp. 101–113

Publisher

Elsevier

Publication Date

January 1, 2013

DOI

10.1016/j.comptc.2012.09.030

ISSN

2210-271X

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