Year: 2009
Type: article
Abstract: 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.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.3237029
Authors: Takashi Tsuchimochi, Gustavo E. Scuseria
Institution: Rice University
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W1966686556