Potential Energy Barrier for Proton Transfer in Compressed Benzoic Acid

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Apr 15

PMID 35425083

Authors

Dominik Kurzydlowski

Affiliations

Soon will be listed here.

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.

Citing Articles

The curious case of proton migration under pressure in the malonic acid and 4,4'-bipyridine cocrystal.

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PMID: 38275161 PMC: 10916288. DOI: 10.1107/S2052252524000344.

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