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Ab initio correlation functionals from second-order perturbation theory

J. Chem. Phys. 125, 104108 (2006); doi:10.1063/1.2212936

Published 12 September 2006

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Igor V. Schweigert, Victor F. Lotrich, and Rodney J. Bartlett
Quantum Theory Project, University of Florida, Gainesville, Florida 32611
Orbital-dependent exchange-correlation functionals are not limited by the explicit dependence on the density and present an attractive alternative to conventional functionals. With the successful implementation of the exact orbital-dependent exchange functional, the challenge lies in developing orbital-dependent approximations for the correlation functional. Ab initio many-body methods can provide such approximations. In particular, perturbation theory with the Kohn-Sham model as the reference [Görling and Levy, Phys. Rev. A 50, 196 (1994)] defines the exact correlation functional via an infinite perturbation series. The second-order term of these series gives the lowest-order approximation to the correlation functional. However, it has been suggested [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)] that the Kohn-Sham Hamiltonian is not the optimal choice for the perturbation expansion and a different reference Hamiltonian may lead to an improved perturbation series and more accurate second-order approximation. Here, we demonstrate explicitly that the modified series can be used to define superior functional and potential. We present results of atomic and molecular calculations with both second-order functionals. Our results demonstrate that the modified functional offers a significantly improved description of the correlation effects as it does not suffer from convergence problems and results in energies and densities that are more accurate than those obtained with second-order Møller-Plesset perturbation theory or generalized-gradient approximation functionals. ©2006 American Institute of Physics
History: Received 8 March 2006; accepted 17 May 2006; published 12 September 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/104108/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ar
    Ab initio calculations (atoms and molecules)
  • 31.15.Md
    Perturbation theory (atoms and molecules)
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • 31.25.-v
    Electron correlation calculations for atoms and molecules
  • YEAR: 2006

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (56)
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