First-principles molecular dynamics simulation of atmospherically relevant anion solvation in supercooled water droplet

We present a comprehensive first-principles Born-Oppenheimer molecular dynamics (BOMD) simulation study of halide anion solvation in a deeply supercooled water droplet (with diameter ∼1.8 nm). We show that larger halide anions Br^- and I^- show "outer-layer surface preference", whereas F^- exhibits bulk preference. Contrary to behavior of other halide anions, Cl^- in the water droplet appears to exhibit no strong tendency of surface or bulk preference at either the supercooled or ambient condition, a phenomenon not previously reported in the literature. BOMD simulation indicates that fully hydrated complex of F ^- is mainly five-fold coordinated (showing square pyramid structure), whereas Cl^-, Br^- and I^- hydrated complexes are either five- or six-fold coordinated (showing sandwich-like structure). Among Cl^-, Br^- and I^- anions, BOMD simulation indicates that I^- exhibits the largest diffusion coefficient despite its largest size. However, computed resident time of the four halide ions suggests that Br^- can approach from the interior to the surface of the water droplet at a much faster rate than I^- and Cl^-. © 2013 American Chemical Society.