In this article, we introduce a new method for solving the electronic Schrödinger equation. This new method follows the same idea followed by the mean-field configuration interaction method already developed for molecular vibrations; i.e., groups of electronic degrees of freedom are contracted together in the mean field of the other degrees. If the same partition of electronic degrees of freedom is iterated, a self-consistent field method is obtained. Making coarser partitions (i.e., including more degrees in the same groups) and discarding the high energy states, the full configuration interaction limit can be approached. In contrast with the usual group function theory, no strong orthogonality condition is enforced. We have made use of a generalized version of the fundamental formula defining a Hopf algebra structure to derive Hamiltonian and overlap matrix element expressions which respect the group structure of the wave function as well as its fermionic symmetry. These expressions are amenable to a recursive computation.
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21 May 2006
Research Article|
May 18 2006
The electronic mean-field configuration interaction method. I. Theory and integral formulas Available to Purchase
Patrick Cassam-Chenaï
Patrick Cassam-Chenaï
a)
CNRS-UNSA, Laboratoire de Mathématique J. A. Dieudonné, Faculté des Sciences,
Université de Nice
, Parc Valrose, 06108 Nice Cedex 2, France and Theoretical Chemistry Group, University of Western Australia
, 35 Stirling Hwy, Crawley WA 6009, Australia
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Patrick Cassam-Chenaï
a)
CNRS-UNSA, Laboratoire de Mathématique J. A. Dieudonné, Faculté des Sciences,
Université de Nice
, Parc Valrose, 06108 Nice Cedex 2, France and Theoretical Chemistry Group, University of Western Australia
, 35 Stirling Hwy, Crawley WA 6009, Australiaa)
Electronic mail: [email protected]
J. Chem. Phys. 124, 194109 (2006)
Article history
Received:
December 01 2005
Accepted:
March 21 2006
Citation
Patrick Cassam-Chenaï; The electronic mean-field configuration interaction method. I. Theory and integral formulas. J. Chem. Phys. 21 May 2006; 124 (19): 194109. https://doi.org/10.1063/1.2196039
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