Strong correlations via constrained-pairing mean-field theory
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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- September 2009
- DOI:
- 10.1063/1.3237029
- arXiv:
- arXiv:0904.2010
- Bibcode:
- 2009JChPh.131l1102T
- Keywords:
-
- atomic clusters;
- dissociation;
- HF calculations;
- hydrogen neutral molecules;
- reaction kinetics theory;
- 82.30.Lp;
- 82.20.-w;
- 36.40.Jn;
- Decomposition reactions;
- Chemical kinetics and dynamics;
- Reactivity of clusters;
- Condensed Matter - Materials Science;
- Condensed Matter - Strongly Correlated Electrons
- E-Print:
- 4 pages, 4 figures, revised version for resubmission