Polarization effects for hydrogen-bonded complexes of substituted phenols with water and chloride ion

William L. Jorgensen, Kasper Planeta Kepp, Anastassia N. Alexandrova

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Abstract

Variations in hydrogen-bond strengths are investigated for complexes of nine parasubstituted phenols (XPhOH) with a water molecule and chloride ion. Results from ab initio HF/6-311+G(d, p) and MP2/6-311+G(d, p)//HF/6-311+G(d, p) calculations are compared with those from the OPLS-AA and OPLS/CM1A force fields. In the OPLS-AA model, the partial charges on the hydroxyl group of phenol are not affected by the choice of para substituent, while the use of CM1A charges in the OPLS/CM1A approach does provide charge redistribution. The ab initio calculations reveal a 2.0-kcal/mol range in hydrogen-bond strengths for the XPhOH... OH2 complexes in the order X = NO2 > CN > CF3 > Cl > F > H > OH > CH3 > NH2. The pattern is not well-reproduced with OPLS-AA, which also compresses the variation to 0.7 kcal/mol. However, the OPLS/CM1A results are in good accord with the ab initio findings for both the ordering and range, 2.3 kcal/mol. The hydrogen bonding is, of course, weaker with XPhOH as acceptor, the order for X is largely inverted, and the range is reduced to ca. 1.0 kcal/mol. The substituent effects are found to be much greater for the chloride ion complexes with a range of 11 kcal/mol. For quantitative treatment of such strong ion-molecule interactions the need for fully polarizable force fields is demonstrated.
Original languageEnglish
JournalJournal of Chemical Theory and Computation
Volume3
Issue number6
Pages (from-to)1987-1992
ISSN1549-9618
DOIs
Publication statusPublished - 2007
Externally publishedYes

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