A size extensive energy functional derived from a double configuration interaction approach: the role of N representability conditions.
Starting from a configuration interaction (CI) approach including only doubly excited configurations, the corresponding energy functional is modified by introduction of a topological factor in the normalization condition of the CI coefficients in such a way that it gets inherently size extensive. Constraints imposed by N representability conditions on the modified functional are discussed and lead to a specific choice of the topological factor. The basic variable in the modified energy functional is the second-order reduced density matrix parametrized in terms of CI-like coefficients. Test calculations for a variety of small molecules show that the numerical results obtained with the new functional are in very good agreement with those obtained from coupled cluster singles doubles calculations.
Kollmar
Christian
C
Lehrstuhl für Theoretische Chemie, Universität Erlangen, Egerlandstrasse 3, D-91058 Erlangen, Germany. christian.kollmar@chemie.uni-erlangen