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Quantum Monte Carlo calculations of the dissociation energies of three-electron hemibonded radical cationic dimers

J. Chem. Phys. 124, 024318 (2006); doi:10.1063/1.2150818

Published 12 January 2006

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I. G. Gurtubay, N. D. Drummond, M. D. Towler, and R. J. Needs
Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, J. J. Thompson Avenue, Cambridge CB3 0HE, United Kingdom
We report variational and diffusion quantum Monte Carlo (VMC and DMC) calculations of the dissociation energies of the three-electron hemibonded radical cationic dimers of He, NH3, H2O, HF, and Ne. These systems are particularly difficult for standard density-functional methods such as the local-density approximation and the generalized gradient approximation. We have performed both all-electron (AE) and pseudopotential (PP) calculations using Slater-Jastrow wave functions with Hartree-Fock single-particle orbitals. Our results are in good agreement with coupled-cluster CCSD(T) calculations. We have also studied the relative stability of the hemibonded and hydrogen-bonded water radical dimer isomers. Our calculations indicate that the latter isomer is more stable, in agreement with post-Hartree-Fock methods. The excellent agreement between our AE and PP results demonstrates the high quality of the PPs used within our VMC and DMC calculations. ©2006 American Institute of Physics
History: Received 28 October 2005; accepted 17 November 2005; published 12 January 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/024318/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Pf
    Variational techniques (atoms and molecules)
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • 31.15.Ne
    Self-consistent-field methods (atoms and molecules)
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • YEAR: 2006

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