Hydration of clays at the molecular scale: the promising perspective of classical density functional theory

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TitleHydration of clays at the molecular scale: the promising perspective of classical density functional theory
Publication TypeJournal Article
Year of Publication2014
AuthorsJeanmairet, G, Marry V, Levesque M, Rotenberg B, Borgis D
JournalMolecular Physics
Volume112
Issue9-10
Start Page1320
Pagination1320 - 1329
Date Published05/2014
Type of ArticleInvited paper for the special edition in honour of Pierre Turq
ISSN1362-3028
Keywordsclassical density functional theory, clays, hydration, liquid state theory, MDFT, molecular density functional theory, molecular dynamics, solvation, solvation free energy
Abstract

We report here how the hydration of complex surfaces can be efficiently
studied thanks to recent advances in classical molecular density functional theory.
This is illustrated on the example of the pyrophylite clay.
After presenting the most recent advances, we show that the
strength of this implicit method is that (i) it is in quantitative
or semi-quantitative agreement with reference all-atoms simulations
(molecular dynamics here) for both the solvation structure and energetics,
and that (ii) the computational cost is two to three orders
of magnitude less than in explicit methods. The method remains imperfect,
in that it locally overestimates the polarization of water close to
hydrophylic sites of the clay. The high numerical efficiency of the method
is illustrated and exploited to carry a systematic study of the electrostatic
and van der Waals components of the surface-solvant interactions
within the most popular force field for clays, CLAYFF. Hydration structure
and energetics are found to weakly depend upon the electrostatics.
We conclude on the consequences of such findings on future force-field
development.
 

URLhttp://dx.doi.org/10.1080/00268976.2014.899647
DOI10.1080/00268976.2014.899647
Short TitleMolecular Physics
Refereed DesignationRefereed
Unit: 
UMR 8640