Anti-hermitian contracted schrödinger equation: direct determination of the two-electron reduced density matrices of many-electron molecules.
Two-electron reduced density matrices (2-RDMs) of many-electron molecules are directly determined without calculation of their wave functions by solving the anti-Hermitian contracted Schrödinger equation. Approximation of the 3-RDM in the anti-Hermitian contracted Schrödinger equation by a corrected cumulant expansion [Mazziotti, Phys. Rev. A 60, 3618 (1999)] permits the direct calculation of the energy and 2-RDM with many high-order correlation effects included. The method is illustrated for the molecules BeH2, H2O, NH3, CH4, and CO as well as the dissociation of BH. Correlation energies are obtained within 95%-100% of full-configuration interaction, and 2-RDMs very nearly satisfy known N-representability conditions.
Mazziotti
David A
DA
Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA. damazz@uchicago.edu