Concerted transfer of multiple protons in acid–water clusters: [(HCl)(H2O)]2 and [(HF)(H2O)]4

Abstract

Molecular dynamics simulations using directly ab initio potentials are carried out for the ionically bonded clusters [(Cl⁻)(H₃O⁺)]₂ and [(F⁻)(H₃O⁺)]₄ to explore their transitions to the hydrogen-bonded [(HCl)(H₂O)]₂ and [(HF)(H₂O)]₄ structures during the first picosecond of simulation. Both the ionic and the H-bonded structures that are formed are highly symmetric. It is found that proton transfers are concerted in all trajectories for [(Cl⁻)(H₃O⁺)]₂. For [(F⁻)(H₃O⁺)]₄, the fully concerted mechanism is dominant but partially concerted transfers of two or three protons at the same time also occur. The concerted mechanism also holds for the reverse process of ionization of neutral acid molecules. It is suggested that the high symmetry of the ionic and the H-bonded structures plays a role in the preference for concerted transfers. Possible implications of the results for proton transfers in other systems are discussed.