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Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

Cornell Affiliated Author(s)

Author

R. Sundararaman
D. Gunceler
Tomas Arias

Abstract

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting model with a single solvent-independent parameter: the electron density threshold (nc), and a single solvent-dependent parameter: the dispersion scale factor (s6), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s6 parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies. © 2014 AIP Publishing LLC.

Date Published

Journal

Journal of Chemical Physics

Volume

141

Issue

13

URL

https://www.scopus.com/inward/record.uri?eid=2-s2.0-84907828117&doi=10.1063%2f1.4896827&partnerID=40&md5=975e8571a01712a169bdcfadcd9ad7d3

DOI

10.1063/1.4896827

Group (Lab)

Tomas Arias Group

Funding Source

1053575

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