Hydration of the chloride ion in concentrated aqueous solutions using neutron scattering and molecular dynamics

Abstract

Neutron scattering experiments were performed on 6 m LiCl solutions in order to obtain the solvation structure around the chloride ion. Molecular dynamics simulations on systems mirroring the concentrated electrolyte conditions of the experiment were carried out with a variety of chloride force-fields. In each case the simulations were run with both full ionic charges and employing the electronic continuum correction (implemented through charge scaling) to account effectively for electronic polarisation. The experimental data were then used to assess the successes and shortcomings of the investigated force-fields. We found that due to the very good signal-to-noise ratio in the experimental data, they provide a very narrow window for the position of the first hydration shell of the chloride ion. This allowed us to establish the importance of effectively accounting for electronic polarisation, as well as adjusting the ionic size, for obtaining a force-field which compares quantitatively to the experimental data. The present results emphasise the utility of performing neutron diffraction with isotopic substitution as a powerful tool in gaining insight and examining the validity of force-fields in concentrated electrolyte solutions.

Keywords:

• chloride
• lithium
• neutron scattering
• molecular dynamics
• solution

Acknowledgements

We thank George Neilson for valuable comments, and P.E. Mason thanks S. Rempe and S. Ansell for aiding in the planning stages of this study. We also thank the ILL and its staff for the use of the experimental facilities and allocated beamtime. P. Jungwirth thanks the Academy of Sciences for the Praemium Academie award. E. Pluhařová acknowledges support from the International Max Planck Research School on Dynamical Processes in Atoms, Molecules, and Solids. The access to computing and storage facilities owned by parties and projects contributing to the National Grid Infrastructure MetaCentrum, provided under the program ‘Projects of Large Infrastructure for Research, Development, and Innovations’ (LM2010005) is appreciated.

Additional information

Funding

This work was supported by the Czech Science Foundation [grant number P208/12/G016] and the Czech Ministry of Education [grant number LH12001].