Generalizations of the direct CI method based on the graphical unitary group approach. II. Single and double replacements from any set of reference configurations

Abstract

The direct CI method is generalized to the case of all single and double replacements from an arbitrary set of reference configurations. This is a continuation of the work and ideas presented in an earlier paper on first order wave functions. The analysis is done using the unitary group formulation of the correlation problem, and the resulting method is a combination of the direct CI method and the unitary group approach as formulated particularly by Paldus and Shavitt. The main idea in the present work is the factorization of the coupling coefficients appearing in the direct CI formalism, into a complicated internal part and a simple external part. The general philosophy is like in all direct CI methods to allow long CI expansions by avoiding the storage and retrieval of a large formula tape. The longest CI expansion treated in this paper is an application on the system CH2(3B1)+H2→CH3+H with five reference states, resulting in 16 096 configurations. The barrier height for the reaction is calculated to be 11.3 kcal/mol and predicted to be slightly below 10 kcal/mol.