Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous Solution-Air Interface

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Daub , C D , Hänninen , V & Halonen , L 2019 , ' Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous Solution-Air Interface ' , Journal of Physical Chemistry B , vol. 123 , no. 3 , pp. 729-737 . https://doi.org/10.1021/acs.jpcb.8b10552

Title: Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous Solution-Air Interface
Author: Daub, Christopher D.; Hänninen, Vesa; Halonen, Lauri
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2019-01-24
Language: eng
Number of pages: 9
Belongs to series: Journal of Physical Chemistry B
ISSN: 1520-6106
URI: http://hdl.handle.net/10138/301152
Abstract: We present the results of ab initio molecular dynamics simulations of the solution-air interface of aqueous lithium bromide (LiBr). We find that, in agreement with the experimental data and previous simulation results with empirical polarizable force field models, Br- anions prefer to accumulate just below the first molecular water layer near the interface, whereas Li+ cations remain deeply buried several molecular layers from the interface, even at very high concentration. The separation of ions has a profound effect on the average orientation of water molecules in the vicinity of the interface. We also find that the hydration number of Li+ cations in the center of the slab Na-c,Na-Li+-H2O approximate to 4.7 +/- 0.3, regardless of the salt concentration. This estimate is consistent with the recent experimental neutron scattering data, confirming that results from nonpolarizable empirical models, which consistently predict tetrahedral coordination of Li+ to four solvent molecules, are incorrect. Consequently, disruption of the hydrogen bond network caused by Li+ may be overestimated in nonpolarizable empirical models. Overall, our results suggest that empirical models, in particular nonpolarizable models, may not capture all of the properties of the solution-air interface necessary to fully understand the interfacial chemistry.
Subject: LIQUID-VAPOR INTERFACE
HYDROGEN-BOND DYNAMICS
HYDRATION STRUCTURE
NEUTRON-SCATTERING
ION SOLVATION
WATER
DENSITY
SURFACE
LI+
MONOVALENT
116 Chemical sciences
114 Physical sciences
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