Correlated Proton Transfer Potentials. (HO-H-OH)- and (H2O-H-OH2)+

Document Type

Article

Journal/Book Title

Journal of Molecular Structure: TheoChem

Publication Date

9-1991

Publisher

Elsevier

Volume

234

First Page

373

Last Page

385

Abstract

Potentials are computed for the transfer of a proton between two hydroxide anions in (HO-H-OH) and between two neutral water molecules in (H2O-H-OH2)+ using polarized basis sets of various sizes. SCF transfer barriers are lowered in both complexes by electron correlation. As progressively higher orders of Moller-Plesset perturbation theory are applied, the correction reverses sign and diminishes in magnitude. As a consequence, MP2 results nearly coincide with full fourth-order data. The highest level calculations indicate the transfer barrier of (HO-H-OH) exceeds that of (H2O-H-OH2)+ by 20–30%. The MP4 calculations agree well with coupled cluster CCD + ST results which include single, double, and triple substitutions to high order.

Comments

http://www.sciencedirect.com/science/article/pii/016612809189024U

Publisher PDF is available for download through the link above.

Published by Elsevier in Journal of Molecular Structure.

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