Title of article
A size-consistent approach to strongly correlated systems using a generalized antisymmetrized product of nonorthogonal geminals
Author/Authors
Johnson، نويسنده , , Paul A. and Ayers، نويسنده , , Paul W. and Limacher، نويسنده , , Peter A. and Baerdemacker، نويسنده , , Stijn De and Neck، نويسنده , , Dimitri Van and Bultinck، نويسنده , , Patrick، نويسنده ,
Issue Information
روزنامه با شماره پیاپی سال 2013
Pages
13
From page
101
To page
113
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 Schrِdinger 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.
Keywords
Bethe ansatz , Antisymmetrized product of geminals wavefunctions , Strong electron correlation , Richardson Hamiltonian , Lie Algebraic Hamiltonians , Off-shell Bethe vectors
Journal title
Computational and Theoretical Chemistry
Serial Year
2013
Journal title
Computational and Theoretical Chemistry
Record number
2286037
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