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Intermolecular potentials based on symmetry-adapted perturbation theory with dispersion energies from time-dependent density-functional calculations

J. Chem. Phys. 123, 214103 (2005); doi:10.1063/1.2135288

Published 2 December 2005

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Alston J. Misquitta and Rafal Podeszwa
Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716

Bogumil Jeziorski
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland

Krzysztof Szalewicz
Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716
Recently, three of us have proposed a method [Phys. Rev. Lett. 91, 33201 (2003)] for an accurate calculation of the dispersion energy utilizing frequency-dependent density susceptibilities of monomers obtained from time-dependent density-functional theory (DFT). In the present paper, we report numerical calculations for the helium, neon, water, and carbon dioxide dimers and show that for a wide range of intermonomer separations, including the van der Waals and short-range repulsion regions, the method provides dispersion energies with accuracies comparable to those that can be achieved using the current most sophisticated wave-function methods. If the dispersion energy is combined with (i) the electrostatic and first-order exchange interaction energies as defined in symmetry-adapted perturbation theory (SAPT) but computed using monomer Kohn-Sham (KS) determinants, and (ii) the induction energy computed using the coupled KS static response theory, (iii) the exchange-induction and exchange-dispersion energies computed using KS orbitals and orbital energies, the resulting method, denoted by SAPT(DFT), produces very accurate total interaction potentials. For the helium dimer, the only system with nearly exact benchmark values, SAPT(DFT) reproduces the interaction energy to within about 2% at the minimum and to a similar accuracy for all other distances ranging from the strongly repulsive to the asymptotic region. For the remaining systems investigated by us, the quality of the SAPT(DFT) interaction energies is so high that these energies may actually be more accurate than the best available results obtained with wave-function techniques. At the same time, SAPT(DFT) is much more computationally efficient than any method previously used for calculating the dispersion and other interaction energy components at this level of accuracy. ©2005 American Institute of Physics
History: Received 14 January 2005; accepted 13 October 2005; published 2 December 2005
Permalink: http://link.aip.org/link/?JCPSA6/123/214103/1
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Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 34.20.Gj
    Intermolecular and atom–molecule potentials and forces
  • 31.15.Md
    Perturbation theory (atoms and molecules)
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • YEAR: 2005

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