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Constrained-pairing mean-field theory. II. Exact treatment of dissociations to nondegenerate orbitals

J. Chem. Phys. 131, 164119 (2009); doi:10.1063/1.3257965

Published 30 October 2009

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Gustavo E. Scuseria1,2 and Takashi Tsuchimochi1
1Department of Chemistry, Rice University, Houston, Texas 77005, USA
2Department of Physics and Astronomy, Rice University, Houston, Texas 77005, USA
Our recently proposed constrained-pairing mean-field theory (CPMFT) is here extended to deal with dissociation of electron pairs to nondegenerate orbitals. To achieve this goal, we introduce the concept of asymptotic constraints. This extended CPMFT model can exactly dissociate polyatomic molecules to restricted open-shell atoms or fragments. We present benchmarks showing how CPMFT accounts for static correlation in an accurate yet computationally inexpensive mean-field manner, while preserving space and spin symmetries. The key element of our approach is the admittance of electron number fluctuations into the wave function. ©2009 American Institute of Physics
History: Received 23 August 2009; accepted 13 October 2009; published 30 October 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/164119/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.vq
    Electron correlation calculations for polyatomic molecules
  • 31.15.xr
    Self-consistent-field methods in atomic and molecular physics
  • 34.50.Gb
    Electronic excitation and ionization of molecules
  • YEAR: 2009

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (14)
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