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

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 (n c), and a single solvent-dependent parameter: the dispersion scale factor (s 6), 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 s 6 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.

Authors:
; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1370466
DOE Contract Number:  
SC0001086
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 13; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Sundararaman, Ravishankar, Gunceler, Deniz, and Arias, T. A. Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models. United States: N. p., 2014. Web. doi:10.1063/1.4896827.
Sundararaman, Ravishankar, Gunceler, Deniz, & Arias, T. A. Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models. United States. doi:10.1063/1.4896827.
Sundararaman, Ravishankar, Gunceler, Deniz, and Arias, T. A. Tue . "Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models". United States. doi:10.1063/1.4896827.
@article{osti_1370466,
title = {Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models},
author = {Sundararaman, Ravishankar and Gunceler, Deniz and Arias, T. A.},
abstractNote = {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.},
doi = {10.1063/1.4896827},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 141,
place = {United States},
year = {2014},
month = {10}
}

Works referenced in this record:

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
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Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

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