Chloride ions as integral parts of hydrogen bonded networks in aqueous salt solutions: the appearance of solvent separated anion pairs.

Phys Chem Chem Phys

Wigner Research Centre for Physics, Konkoly Thege út 29-33, H-1121 Budapest, Hungary. and International Research Organisation for Advanced Science and Technology (IROAST), Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.

Published: May 2020

Hydrogen bonding to chloride ions has been frequently discussed over the past 5 decades. Still, the possible role of such secondary intermolecular bonding interactions in hydrogen bonded networks has not been investigated in any detail. Here we consider computer models of concentrated aqueous LiCl solutions and compute the usual hydrogen bond network characteristics, such as distributions of cluster sizes and of cyclic entities, both for models that take and do not take chloride ions into account. During the analysis of hydrogen bonded rings, a significant amount of 'solvent separated anion pairs' have been detected at high LiCl concentrations. It is demonstrated that taking halide anions into account as organic constituents of the hydrogen bonded network does make the interpretation of structural details significantly more meaningful than when considering water molecules only. Finally, we compare simulated structures generated by 'good' and 'bad' potential sets on the basis of the tools developed here, and show that this novel concept is, indeed, also helpful for distinguishing between reasonable and meaningless structural models.

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http://dx.doi.org/10.1039/d0cp01806fDOI Listing

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