Probing the Role of Solvent Configurations and Local Electric Fields on HX (X = F, Cl, Br and I) Dissociation in Water Clusters

The acidity of hydrohalic acids increases down the group, with HF and HI being the weakest and strongest acids. Electronic structure calculations suggest that the critical electric fields required for the dissociation of HF, HCl, HBr, and HI are 347, 193, 163, and 153 MV cm^-1, respectively, which are proportional to their corresponding p<i>K</i>_a values and emphasize that in these systems the bond dissociation energy determines the p<i>K</i>_a. The solvent configuration plays a significant role in the acid dissociation process, which is illustrated by a particular configuration of three water molecules around HX and favors dissociation of only HBr, even though the critical electric field required for the dissociation of HI is lower than that of HBr, as depicted in the graphical abstract. Further, the Born-Oppenheimer molecular dynamics (BOMD) simulations suggest that the spontaneity of HX dissociation depends on both the solvent configuration and thermal fluctuations, which hold higher significance in the case of weaker acids. In general, it was observed that the solvent electric field required for the acid dissociation process is marginally lower at higher temperatures.