Published in

American Chemical Society, The Journal of Physical Chemistry A, 27(112), p. 6171-6178, 2008

DOI: 10.1021/jp802272r

Links

Tools

Export citation

Search in Google Scholar

Influence of Structure on Electron Correlation Effects and Electron−Water Dispersion Interactions in Anionic Water Clusters

Journal article published in 2008 by Christopher F. Williams, John M. Herbert ORCID
This paper was not found in any repository; the policy of its publisher is unknown or unclear.
This paper was not found in any repository; the policy of its publisher is unknown or unclear.

Full text: Unavailable

Green circle
Preprint: archiving allowed
  • Must obtain written permission from Editor
  • Must not violate ACS ethical Guidelines
Orange circle
Postprint: archiving restricted
  • Must obtain written permission from Editor
  • Must not violate ACS ethical Guidelines
Red circle
Published version: archiving forbidden
Data provided by SHERPA/RoMEO

Abstract

Electronic structure calculations at the level of second-order Møller-Plesset perturbation theory have been performed on anionic water clusters, (H2O)n(-), in the n = 14-33 size regime. The contribution to the electron binding energy that arises from electron correlation is found to be significantly larger for cavity-bound electrons than it is for surface-bound electrons, even for surface states with electron binding energies well above 1 eV. A decomposition of the correlation energy into interactions between pairs of Boys-localized molecular orbitals is used to demonstrate that the larger correlation energy found in the cavity isomers arises from electron-water dispersion interactions, and that the dispersion interaction is larger in cavity-bound isomers because the unpaired electron penetrates well beyond the first solvation shell. In contrast, a surface-bound electron exhibits virtually no penetration into the interior of the cavity. To obtain a qualitatively accurate picture of this phenomenon, one must plot molecular orbitals using isoprobability surfaces rather than arbitrarily-selected isocontours.