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research article

Soft-Sphere Continuum Solvation in Electronic-Structure Calculations

Fisicaro, Giuseppe
•
Genovese, Luigi
•
Andreussi, Oliviero  
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2017
Journal of Chemical Theory and Computation

We present an implicit solvation approach where the interface-between the quantum-mechanical solute and the surrounding environment is, described by a fully continuous permittivity built up with atomic-centered "soft" spheres. This approach combines many of-the advantages the self-consistent continuum solvation model, in-handling solutes and surfaces in contact with complex dielectric environments or electrolytes in electronic-structure calculations. In addition it is able to describe accurately both neutral and charged systems. The continuous function, describing the variation of the permittivity, allows, to compute analytically the nonelectrostatic contributions to the solvation free energy that are described in terms of the quantum surface. The whole methodology is computationally stable, provides consistent energies and forces, and keeps the computational efforts and runtimes comparable to those of standard vacuum calculations. The capability to treat arbitrary molecular or slab-like geometries as well as charged Molecules is key to tackle electrolytes within mixed frameworks. We show that, with given, fixed atomic radii, two parameters are sufficient to give a mean absolute error of only 1.12 kcal/mol with respect to the experimental aqueous solvation energies for a set of 274 neutral solutes. For charged systems, the same set of parameters provides solvation energies for a set of 60 anions and 52 cations with an error of 2.96 and 2.13 kcal/mol, respectively, improving upon previous literature values. To tackle elements not present in most solvation databases, a new benchmark scheme On wettability and contact angles is proposed for solid-liquid interfaces and applied to the investigation of the stable terminations of a CdS (11 (2) over bar0) surface in an electrochemical medium.

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Type
research article
DOI
10.1021/acs.jctc.7b00375
Web of Science ID

WOS:000407522100033

Author(s)
Fisicaro, Giuseppe
Genovese, Luigi
Andreussi, Oliviero  
Mandal, Sagarmoy
Nair, Nisanth N.
Marzari, Nicola  
Goedecker, Stefan
Date Issued

2017

Publisher

Amer Chemical Soc

Published in
Journal of Chemical Theory and Computation
Volume

13

Issue

8

Start page

3829

End page

3845

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
September 5, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/140119
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