Acid Dissociation in HCl-Water Clusters is Temperature Dependent and Cannot be Detected Based on Dipole Moments

The dissociation of acids in aqueous environments at low temperatures in the presence of a limited amount of water is underlying a wealth of processes from atmospheric to interstellar science. For the paradigmatic case of HCl(H2O)(n) clusters, our extensive ab initio path integral simulations quantify in terms of free energy differences and barriers that n = 4 water molecules are indeed required to dissociate HCl at low temperatures. Increasing the temperature, however, reverses the process and thus counteracts dissociation by fluctuation-driven recombination. The size of the electric dipole moment is shown to not correlate with the acid being in its dissociated or molecular state, thus rendering its measurement as a function of n unable to detect the dissociation transition.