Static Correlation via Constrained-Pairing Mean-Field Theory

Abstract

I will present a mean-field approach for accurately describing strong correlations via electron number fluctuations and pairings constrained to an active space. Electron number conservation is broken and correct only on average but both spin and spatial symmetries are preserved. Optimized natural orbitals and occupations are determined by diagonalization of a mean-field Hamiltonian. This constrained-pairing mean-field theory (CPMFT) yields a two-particle density matrix ansatz that seems to exclusively describe static correlation. I will demonstrate CPMFT accuracy with applications to the metal-insulator transition of large hydrogen clusters and molecular dissociation curves. I will also discuss the inclusion of dynamical correlation effects via traditional density functionals