A new proposal for determining CI quasi-diabatic states, potential energy surfaces and electronic couplings is introduced using the quasi-degenerate perturbation theory (QDPT) ; zeroth-order CI adiabatic states, resulting from a partial diagonalisation, are submitted to a unitary transformation in order to yield quasi-diabatic states presenting the maximum overlap with an external set of independent diabatic reference functions. An effective Hamiltonian in the quasi-diabatic representation is then obtained by applying the QDPT in the model space spanned by the quasi-diabatic states. This algorithm is exemplified by the HeNe2+ 1Sigma+ states for which the dynamical couplings are computed using finite difference techniques combined with first-order transition density matrices.

Quasi--diabatic states and dynamical couplings from ab initio CI calculations: a new proposal

CIMIRAGLIA, Renzo;
1985

Abstract

A new proposal for determining CI quasi-diabatic states, potential energy surfaces and electronic couplings is introduced using the quasi-degenerate perturbation theory (QDPT) ; zeroth-order CI adiabatic states, resulting from a partial diagonalisation, are submitted to a unitary transformation in order to yield quasi-diabatic states presenting the maximum overlap with an external set of independent diabatic reference functions. An effective Hamiltonian in the quasi-diabatic representation is then obtained by applying the QDPT in the model space spanned by the quasi-diabatic states. This algorithm is exemplified by the HeNe2+ 1Sigma+ states for which the dynamical couplings are computed using finite difference techniques combined with first-order transition density matrices.
1985
Cimiraglia, Renzo; J., Malrieu; M., Persico; F., Spiegelmann
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/1808733
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