Ab Initio Molecular Dynamics Simulations of the Influence of Lithium Bromide on the Structure of the Aqueous...

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 N_c,Li ≈ 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.