Double proton transfer in formic, thioformic and dithioformic acid dimers: An energetic, mechanistic and kinetic investigation

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-03-03 DOI:10.1016/j.comptc.2025.115164

Monu , Binod Kumar Oram , Ankita Kothari , Biman Bandyopadhyay

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Abstract

A quantum chemical investigation of energetic, mechanistic, and kinetic aspects of the double proton transfer reactions in homogenous and mixed dimers of formic acids and its mono and dithio derivatives have been studied employing CCSD(T)-F12/cc-pVTZ-F12//ωB97X-D/aug-cc-pV(D + d)Z level of theory. The findings agree closely with existing results for formic acid dimer. A total of ten dimers, 4 homogeneous and 6 mixed, have been studied and 7 transition states have been identified. The bimolecular proton transfer barriers vary linearly with the binding energies of the dimers. Reaction force and Wiberg bond index analyses show that proton transfers in homogeneous dimers are synchronous, whereas the same in mixed dimers are asynchronous; The latter type of proton transfer is always initiated by dissociation of SH bond. The bimolecular rate constant of proton transfer exhibits a systematic dependence on the barrier height, supporting the observed correlation between the barrier height and binding energy.

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甲酸、硫代甲酸和二硫代甲酸二聚体中的双质子转移：能量、机理和动力学研究

采用CCSD(T)-F12/cc-pVTZ-F12//ωB97X-D/奥格-cc- pv (D + D)Z能级理论研究了甲酸均相和混合二聚体及其单硫和双硫衍生物双质子转移反应的能量、机理和动力学。这些发现与甲酸二聚体的现有结果非常一致。共研究了10种二聚体，其中4种为均匀二聚体，6种为混合二聚体，确定了7种过渡态。双分子质子转移势垒随二聚体的结合能呈线性变化。反作用力和Wiberg键指数分析表明，均相二聚体的质子转移是同步的，而混合二聚体的质子转移是异步的；后一种质子转移通常是由SH键离解引起的。质子转移的双分子速率常数系统地依赖于势垒高度，支持所观察到的势垒高度与结合能之间的相关性。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.