Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 112, Issue 27, Pages 6171-6178Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp802272r
Keywords
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Funding
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0748448] Funding Source: National Science Foundation
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Electronic structure calculations at the level of second-order Moller-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 impaired 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.
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