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The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model

Sundararaman, Ravishankar and Goddard, William A., III (2015) The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model. Journal of Chemical Physics, 142 (6). Art. No. 064107. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20150402-091624373

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Abstract

Many important applications of electronic structure methods involve molecules or solid surfaces in a solvent medium. Since explicit treatment of the solvent in such methods is usually not practical, calculations often employ continuum solvation models to approximate the effect of the solvent. Previous solvation models either involve a parametrization based on atomic radii, which limits the class of applicable solutes, or based on solute electron density, which is more general but less accurate, especially for charged systems. We develop an accurate and general solvation model that includes a cavity that is a nonlocal functional of both solute electron density and potential, local dielectric response on this nonlocally determined cavity, and nonlocal approximations to the cavity-formation and dispersion energies. The dependence of the cavity on the solute potential enables an explicit treatment of the solvent charge asymmetry. With four parameters per solvent, this “CANDLE” model simultaneously reproduces solvation energies of large datasets of neutral molecules, cations, and anions with a mean absolute error of 1.8 kcal/mol in water and 3.0 kcal/mol in acetonitrile.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.4907731 DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/142/6/10.1063/1.4907731PublisherArticle
http://arxiv.org/abs/1410.2922arXivDiscussion Paper
ORCID:
AuthorORCID
Sundararaman, Ravishankar0000-0002-0625-4592
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2015 AIP Publishing LLC. Received 10 October 2014; accepted 27 January 2015; published online 11 February 2015. We thank Yan-Choi Lam, Dr. Robert Nielsen, and Dr. Yuan Ping for suggesting benchmark systems, for help locating experimental data, and for useful discussions. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1108
Issue or Number:6
Record Number:CaltechAUTHORS:20150402-091624373
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150402-091624373
Official Citation:The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model Sundararaman, Ravishankar and Goddard, William A., The Journal of Chemical Physics, 142, 064107 (2015), DOI:http://dx.doi.org/10.1063/1.4907731
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56304
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Apr 2015 18:41
Last Modified:03 Oct 2019 08:12

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