Kurzydłowski Dominik
Faculty of Mathematics and Natural Sciences, Cardinal Stefan Wyszyński University in Warsaw 01-038 Warsaw Poland
RSC Adv. 2022 Apr 12;12(18):11436-11441. doi: 10.1039/d2ra01736a. eCollection 2022 Apr 7.
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.
苯甲酸（BA）是用于研究质子转移（PT）反应的模型体系。由于存在通过压缩调节PT势垒的可能性，因此受到高压（超过1 kbar = 0.1 GPa）作用的固态BA的性质特别令人感兴趣。在此，我们展示了旨在评估在1个大气压至15 GPa压力范围内固态BA中该势垒值的模拟。我们发现，BA二聚体内O⋯O接触因压力而缩短，导致PT势垒降低，以及氢键随后的对称化。然而，只有在考虑BA互变异构体与过渡态之间的零点能（ZPE）差异之后，才会出现这种效应。所得结果为先前关于压缩苯甲酸的实验提供了启示，并表明关于O⋯O距离的常见标度行为可能适用于有机和无机体系中的氢键对称化。
