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Journal of Chemical Physics / Volume 124 / Issue 2 / ARTICLES / Gas Phase Dynamics and Structure: Spectroscopy, Molecular Interactions, Scattering, and Photochemistry

J. Chem. Phys. 124, 024318 (2006); http://dx.doi.org/10.1063/1.2150818 (6 pages)

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

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

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(Received 28 October 2005; accepted 17 November 2005; published online 12 January 2006)

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

Article Outline

  1. INTRODUCTION
  2. VMC AND DMC METHODS
  3. RESULTS
    1. Dissociation energies of the radical dimers
    2. Relative stability of hemibonded and hydrogen-bonded water radical dimers
    3. Spin density of the radical dimers
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

helium neutral atoms, water, ammonia, hydrogen compounds, neon, free radicals, Monte Carlo methods, variational techniques, dissociation energies, density functional theory, pseudopotential methods, HF calculations, STO calculations, wave functions, hydrogen bonds, isomerism

PACS

  • 31.15.xt

    Variational techniques

  • 31.15.E-

    Density-functional theory

  • 33.15.Fm

    Bond strengths, dissociation energies

  • 31.15.xr

    Self-consistent-field methods

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2150818

PUBLICATION DATA

ISSN

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

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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