Title

Spatial and Spin Symmetry Breaking in Semidefinite-Programming-Based Hartree-Fock Theory

Abstract

The Hartree-Fock problem was recently recast as a semidefinite optimization over the space of rank-constrained two-body reduced-density matrices (RDMs) [ Phys. Rev. A 2014, 89, 010502(R) ]. This formulation of the problem transfers the nonconvexity of the Hartree-Fock energy functional to the rank constraint on the two-body RDM. We consider an equivalent optimization over the space of positive semidefinite one-electron RDMs (1-RDMs) that retains the nonconvexity of the Hartree-Fock energy expression. The optimized 1-RDM satisfies ensemble N-representability conditions, and ensemble spin-state conditions may be imposed as well. The spin-state conditions place additional linear and nonlinear constraints on the 1-RDM. We apply this RDM-based approach to several molecular systems and explore its spatial (point group) and spin (Ŝ2 and Ŝ3) symmetry breaking properties. When imposing Ŝ2 and Ŝ3 symmetry but relaxing point group symmetry, the procedure often locates spatial-symmetry-broken solutions that are difficult to identify using standard algorithms. For example, the RDM-based approach yields a smooth, spatial-symmetry-broken potential energy curve for the well-known Be-H2 insertion pathway. We also demonstrate numerically that, upon relaxation of Ŝ2 and Ŝ3 symmetry constraints, the RDM-based approach is equivalent to real-valued generalized Hartree-Fock theory.

Publication Title

Journal of Chemical Theory and Computation

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