Multi-state multi-reference Møller-Plesset second-order perturbation theory for molecular calculations

Jan Franz

doi:10.1002/qua.20848

Multi-state multi-reference Møller-Plesset second-order perturbation theory for molecular calculations

Abstract

This work presents multi‐state multi‐reference Møller–Plesset second‐order perturbation theory as a variant of multi‐reference perturbation theory to treat electron correlation in molecules. An effective Hamiltonian is constructed from the first‐order wave operator to treat several strongly interacting electronic states simultaneously. The wave operator is obtained by solving the generalized Bloch equation within the first‐order interaction space using a multi‐partitioning of the Hamiltonian based on multi‐reference Møller–Plesset second‐order perturbation theory. The corresponding zeroth‐order Hamiltonians are nondiagonal. To reduce the computational effort that arises from the nondiagonal generalized Fock operator, a selection procedure is used that divides the configurations of the first‐order interaction space into two sets based on the strength of the interaction with the reference space. In the weaker interacting set, only the projected diagonal part of the zeroth‐order Hamiltonian is taken into account. The justification of the approach is demonstrated in two examples: the mixing of valence Rydberg states in ethylene, and the avoided crossing of neutral and ionic potential curves in LiF

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Author (1)

Jan Franz dr hab.
- Universitat Bonn Institut fu¨r Physikalische und Theoretische Chemie

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Category:: Articles
Type:: artykuł w czasopiśmie wyróżnionym w JCR
Published in:: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY no. 106, edition 4, pages 773 - 786,
ISSN: 0020-7608
Language:: English
Publication year:: 2006
Bibliographic description:: Franz J.: Multi-state multi-reference Møller-Plesset second-order perturbation theory for molecular calculations// INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY. -Vol. 106, iss. 4 (2006), s.773-786
DOI:: Digital Object Identifier (open in new tab) 10.1002/qua.20848
Verified by:: Gdańsk University of Technology