Strong correlations via constrained-pairing mean-field theory.
We 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 exclusively describes strong correlations. We demonstrate CPMFT accuracy with applications to the metal-insulator transition of large hydrogen clusters and molecular dissociation curves.
Tsuchimochi
Takashi
T
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
Scuseria
Gustavo E
GE