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Ab initio density functional theory: The best of both worlds?

J. Chem. Phys. 123, 062205 (2005); doi:10.1063/1.1904585

Published 17 August 2005

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Rodney J. Bartlett, Victor F. Lotrich, and Igor V. Schweigert
Quantum Theory Project, Departments of Chemistry and Physics, University of Florida, Gainesville, Florida 32611
Density functional theory (DFT), in its current local, gradient corrected, and hybrid implementations and their extensions, is approaching an impasse. To continue to progress toward the quality of results demanded by today's ab initio quantum chemistry encourages a new direction. We believe ab initio DFT is a promising route to pursue. Whereas conventional DFT cannot describe weak interactions, photoelectron spectra, or many potential energy surfaces, ab initio DFT, even in its initial, optimized effective potential, second-order many-body perturbation theory form [OEP (2)-semi canonical], is shown to do all well. In fact, we obtain accuracy that frequently exceeds MP2, being competitive with coupled-cluster theory in some cases. Furthermore, this is accomplished within a relatively fast computational procedure that scales like iterative second order. We illustrate our results with several molecular examples including Ne2,Be2,F2, and benzene. ©2005 American Institute of Physics
History: Received 4 June 2004; accepted 17 March 2005; published 17 August 2005
Permalink: http://link.aip.org/link/?JCPSA6/123/062205/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ar
    Ab initio calculations (atoms and molecules)
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • 31.15.Md
    Perturbation theory (atoms and molecules)
  • 31.15.Dv
    Coupled cluster theory (atoms and molecules)
  • YEAR: 2005

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