Testing the parametric two-electron reduced-density-matrix method with improved functionals: Application to the conversion of hydrogen peroxide to oxywater

摘要

Parametrization of the two-electron reduced density matrix (2-RDM) has recently enabled the direct calculation of electronic energies and 2-RDMs at the computational cost of configuration interaction with single and double excitations. While the original Kollmar energy functional yields energies slightly better than those from coupled cluster with single-double excitations, a general family of energy functionals has recently been developed whose energies approach those from coupled cluster with triple excitations D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008). In this paper we test the parametric 2-RDM method with one of these improved functionals through its application to the conversion of hydrogen peroxide to oxywater. Previous work has predicted the barrier from oxywater to hydrogen peroxide with zero-point energy correction to be 3.3-to-3.9 kcal/mol from coupled cluster with perturbative triple excitations CCSD(T) and -2.3 kcal/mol from complete active-space second-order perturbation theory (CASPT2) in augmented polarized triple-zeta basis sets. Using a larger basis set than previously employed for this reaction-an augmented polarized quadruple-zeta basis set (aug-cc-pVQZ)-with extrapolation to the complete basis-set limit, we examined the barrier with two parametric 2-RDM methods and three coupled cluster methods. In the basis-set limit the M parametric 2-RDM method predicts an activation energy of 2.1 kcal/mol while the CCSD(T) barrier becomes 4.2 kcal/mol. The dissociation energy of hydrogen peroxide to hydroxyl radicals is also compared to the activation energy for oxywater formation. We report energies, optimal geometries, dipole moments, and natural occupation numbers. Computed 2-RDMs nearly satisfy necessary N-representability conditions.