Closed-form expressions for correlated density matrices: application to dispersive interactions and example of He2.
Empirically correlated density matrices of N-electron systems are investigated. Closed-form expressions are derived for the one- and two-electron reduced density matrices from a pairwise correlated wave function. Approximate expressions are then proposed which reflect dispersive interactions between closed-shell centrosymmetric subsystems. Said expressions clearly illustrate the consequences of second-order correlation effects on the reduced density matrices. Application is made to a simple example: the He(2) system. Reduced density matrices are explicitly calculated, correct to second order in correlation, and compared with approximations of independent electrons and independent electron pairs. The models proposed allow for variational calculations of interaction energies and equilibrium distance as well as a clear interpretation of dispersive effects on electron distributions. Both exchange and second order correlation effects are shown to play a critical role on the quality of the results.
Ragot
Sébastien
S
Laboratoire Structure, Propriété Modélisation des Solides (CNRS, Unité Mixte de Recherche 85-80), Ecole Centrale Paris, Grande Voie des Vignes, 92295 Chatenay-Malabry, France. at_home@club-internet.fr
Becker
Pierre J
PJ