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Dissociation energy of the water dimer from quantum Monte Carlo calculations

J. Chem. Phys. 127, 124306 (2007); doi:10.1063/1.2770711

Published 25 September 2007

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I. G. Gurtubay
Theory of Condensed Matter Group, Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom and Materia Kondentsatuaren Fisika Saila, Zientzia eta Teknologia Fakultatea, Euskal Herriko Unibertsitatea, 644 Posta Kutxatila, E-48080 Bilbo, Basque Country, Spain

R. J. Needs
Theory of Condensed Matter Group, Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom
We report a study of the electronic dissociation energy of the water dimer using quantum Monte Carlo techniques. We have performed variational quantum Monte Carlo and diffusion quantum Monte Carlo (DMC) calculations of the electronic ground state of the water monomer and dimer using all-electron and pseudopotential approaches. We have used Slater-Jastrow trial wave functions with B3LYP type single-particle orbitals, into which we have incorporated backflow correlations. When backflow correlations are introduced, the total energy of the water monomer decreases by about 4–5  mhartree, yielding a DMC energy of −76.428  30(5)  hartree, which is only 10  mhartree above the experimental value. In our pseudopotential DMC calculations, we have compared the total energies of the water monomer and dimer obtained using the locality approximation with those from the variational scheme recently proposed by Casula [Phys. Rev. B 74, 161102(R) (2006)]. The time step errors in the Casula scheme are larger, and the extrapolation of the energy to zero time step always lies above the result obtained with the locality approximation. However, the errors cancel when energy differences are taken, yielding electronic dissociation energies within error bars of each other. The dissociation energies obtained in our various all-electron and pseudopotential calculations range between 5.03(7) and 5.47(9)  kcal/mol and are in good agreement with experiment. Our calculations give monomer dipole moments which range between 1.897(2) and 1.909(4)  D and dimer dipole moments which range between 2.628(6) and 2.672(5)  D. ©2007 American Institute of Physics
History: Received 30 May 2007; accepted 18 July 2007; published 25 September 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/124306/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Pf
    Variational techniques (atoms and molecules)
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • 33.15.Kr
    Molecular electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
  • YEAR: 2007

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