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Title: Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz

Abstract

Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with a RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.

Authors:
ORCiD logo; ; ;
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:
1370450
DOE Contract Number:
SC0001086
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 5; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, and Arias, T. A. Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz. United States: N. p., 2015. Web. doi:10.1063/1.4906828.
Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, & Arias, T. A. Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz. United States. doi:10.1063/1.4906828.
Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, and Arias, T. A. Sat . "Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz". United States. doi:10.1063/1.4906828.
@article{osti_1370450,
title = {Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz},
author = {Sundararaman, Ravishankar and Schwarz, Kathleen A. and Letchworth-Weaver, Kendra and Arias, T. A.},
abstractNote = {Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with a RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.},
doi = {10.1063/1.4906828},
journal = {Journal of Chemical Physics},
number = 5,
volume = 142,
place = {United States},
year = {Sat Feb 07 00:00:00 EST 2015},
month = {Sat Feb 07 00:00:00 EST 2015}
}