VBSM: A solvation model based on valence bond theory

Peifeng Su, Wei Wu, Casey P. Kelly, Christopher J. Cramer, Donald G. Truhlar

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Abstract

A new solvation model, called VBSM, is presented. The model combines valence bond (VB) theory with parameters determined for the SM6 solvation model (Kelly, C. P.; Cramer, C. J.; Truhlar, D. G. J. Chem. Theo. Comp. 2005, 1, 1133-1152). VBSM, like SM6, is based on the generalized Born (GB) approximation for bulk electrostatics and atomic surface tensions to account for cavitation, dispersion, and solvent structure (CDS). The solvation free energy of VBSM includes (i) a self-consistent polarization term obtained by using VB atomic charges in a GB reaction field with a VB self-consistent field procedure that minimizes the total energy of the system with respect to the valence bond orbitals and (ii) a geometry-dependent CDS term to account for deviations from bulk-electrostatic solvation. Test calculations for a few systems show that the liquid-phase partial atomic charges obtained by VBSM are in good agreement with liquid-phase charges obtained by charge model CM4 (Kelly, C. P.; Cramer, C. J.; Truhlar, D. G.J. Chem. Theo. Comp. 2005, 1, 1133-1152). Free energies of solvation are calculated for two prototype test cases, namely, for the degenerate SN2 reaction of Cl- with CH3Cl in water and for a Menshutkin reaction in water. These calculations show that the VBSM method provides a practical alternative to single-configuration self-consistent field theory for solvent effects in molecules and chemical reactions.

Original languageEnglish (US)
Pages (from-to)12761-12768
Number of pages8
JournalJournal of Physical Chemistry A
Volume112
Issue number50
DOIs
StatePublished - Dec 18 2008

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