Variational Optimization Of The Second Order Density Matrix Derived From A Seniority-Zero Wave Function

W. POELMANS; M. VAN RAEMDONCK; B. VERSTICHEL; S. DE BAERDEMACKER; A. TORRE; L. LAIN; G.E. MASSACCESI; D.R. ALCOBA; P. BULTINCK; D. VAN NECK

JOURNAL OF CHEMICAL THEORY AND COMPUTATION

AMER CHEMICAL SOC

Lugar: Washington; Año: 2015 vol. 11 p. 4064 - 4076

1549-9618

We perform a direct variational determination of the second-order (two-particle) density matrix corresponding to a many-electron system, under a restricted set of the two-index N-representability P-, Q-, and G-conditions. In addition, we impose a set of necessary constraints that the two-particle density matrix must be derivable from a doubly-occupied many-electron wave function, i.e. a singlet wave function for which the Slater determinant decomposition only contains determinants in which spatial orbitals are doubly occupied. We rederive the two-index N-representability conditions first found by Weinhold and Wilson and apply them to various benchmark systems (linear hydrogen chains, He, N2 and CN-). This work is motivated by the fact that a doubly-occupied many-electron wave function captures in many cases the bulk of the static correlation. Compared to the general case, the structure of doubly-occupied two particle density matrices causes the associate semidefinite program to have a very favorable scaling as L3, where L is the number of spatial orbitals. Since the doubly-occupied Hilbert space depends on the choice of the orbitals, variational calculation steps of the two-particle density matrix are interspersed with orbital-optimization steps (based on Jacobi rotations in the space of the spatial orbitals). We also point to the importance of symmetry breaking of the orbitals when performing calculations in a doubly-occupied framework.