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Theoretical study of the binding of the chloride anion to water and alcohols
Author(s) -
Berthier G.,
Savinelli R.,
Pullman A.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)63:2<567::aid-qua26>3.0.co;2-3
Subject(s) - chemistry , basis set , supermolecule , atomic orbital , computational chemistry , gaussian , binding energy , valence (chemistry) , molecular orbital , ion , polarization (electrochemistry) , coulomb , atomic physics , molecule , quantum mechanics , physics , density functional theory , organic chemistry , electron
The binding energies of chloride adducts to water, methanol, and isopropanol have been calculated by the molecular orbital method at the self‐consistent field (SCF) and Möller‐Plesset [MP2, and (partially) MP4] levels. Extended Gaussian basis sets enlarged with both standard valence polarization orbitals and semidiffuse Coulomb polarization orbitals have been used. The best theoretical values obtained by correcting the energy differences between the supermolecule and its fragments for basis‐set superposition errors and zero‐point vibration energies are in satisfactory agreement with the available reaction enthalpies (i.e., 12.4 kcal/mol computed for water, versus 13.1 experimentally). Equally in agreement with the experimental trend, an increase in the binding energy of Cl − is predicted in going from water to alcohols. The proper introduction of correlation in a sufficiently extended and polarized basis set is essential to the reproduction of this trend. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 567–574, 1997