Parametric two-electron reduced-density-matrix method applied to computing molecular energies and properties at nonequilibrium geometries.

A parametric approach to the variational calculation of the two-electron reduced density matrix (2-RDM) for many-electron atoms and molecules has recently been developed in which the 2-RDM is parametrized to be both size consistent and nearly N-representable [C. Kollmar, J. Chem. Phys. 125, 084108 (2006); A. E. DePrince and D. A. Mazziotti, Phys. Rev. A 76, 049903 (2007)]. The parametric variational 2-RDM method is applied to computing ground-state molecular energies and properties at nonequilibrium geometries in significantly larger basis sets than previously employed. We study hydrogen abstraction from the hydroxide groups of H(2)O, NH(3)OH, and CH(3)OH. The 2-RDM method, parametrized by single and double excitations, shows significant improvement over coupled-cluster methods with similar excitations in predicting the shape of potential energy curves and bond-dissociation energies. Previous work completes the parametrization of the energy and 2-RDM by a system of n(2)h(2) normalization constraints, where n and h are the number of occupied and unoccupied orbitals, respectively. In the present paper, however, we show that the constraints can be eliminated by incorporating them into the energy and 2-RDM functions and, hence, the constrained optimization of the ground-state energy can be reformulated as an unconstrained optimization. The 2-RDMs from the parametric method are very nearly N-representable, and as measured by an l(2) norm, they are more accurate than the 2-RDMs from configuration interaction truncated at single and double excitations by an order of magnitude.