Born–Oppenheimer Molecular Dynamics Simulations of a Bromate Ion in Water Reveal Its Dual Kosmotropic and Chaotropic Behavior

Abstract

The solvation structure and dynamics of a bromate (BrO3–) ion in water are studied by means of Born–Oppenheimer molecular dynamics simulations at two different temperatures using the Becke–Lee–Yang–Parr functional with Grimme D3 dispersion corrections. The bromate ion possesses a pyramidal structure, and it has two types of solvation sites, namely, the bromine and oxygen atoms. We have looked at different radial and orientational distributions of water molecules around the bromate ion and also investigated their hydrogen bonding properties. The solvation structure of the bromate ion is also compared with that of the iodate (IO3–) ion, which is structurally rather similar to the bromate ion and was found to have some unusual solvation properties in water. It is found that the bromate ion follows a similar trend as that followed by the iodate ion as far as the solvation structure is concerned. However, the effect of the former on surrounding water is found to be much weaker than that of the latter. On the dynamical side, we have looked at diffusion, residence dynamics, and also the orientational and hydrogen bond relaxation of water molecules around the BrO3– ion and compared them with those of the bulk. Dynamical results are presented for both H2O and D2O around the BrO3– ion. Interpretation of the dynamical results in terms of structure-making (kosmotropic)/-breaking (chaotropic) properties of the BrO3– ion reveals that the bromine atom of this ion acts as a water structure breaker, whereas the three oxygens act as water structure makers. Thus, in spite of being a single ion, the bromate ion has dual characteristics and the experimentally observed kosmotropic ability of this ion is actually a trade-off between a chaotropic site (the bromine atom) and three kosmotropic sites (three oxygen atoms) that are present in the ion.