Potential energy barrier for proton transfer in compressed benzoic acid

Abstract

Benzoic acid (BA) is a model system for studying proton transfer (PT) reactions. The properties of solid BA subject to high pressure (exceeding 1 kbar = 0.1 GPa) are of particular interest due to the possibility of compression-tuning of the PT barrier. Here we present simulations aimed at evaluating the value of this barrier in solid BA in the 1 atm – 15 GPa pressure range. We find that pressure-induced shortening of O⋯O contacts within the BA dimers leads to a decrease in the PT barrier, and subsequent symmetrization of the hydrogen bond. However, this effect is obtained only after taking into account zero-point energy (ZPE) differences between BA tautomers and the transition state. The obtained results shed light on previous experiments on compressed benzoic acid, and indicate that a common scaling behavior with respect to the O⋯O distance might be applicable for hydrogen-bond symmetrization in both organic and inorganic systems.