Tasi Domonkos A, Czakó Gábor
MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre, Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged Rerrich Béla tér 1 Szeged H-6720 Hungary
Chem Sci. 2021 Oct 14;12(43):14369-14375. doi: 10.1039/d1sc03834f. eCollection 2021 Nov 10.
Theoretical investigations on chemical reactions allow us to understand the dynamics of the possible pathways and identify new unexpected routes. Here, we develop a global analytical potential energy surface (PES) for the OH + CHF reaction in order to perform high-level dynamics simulations. Besides bimolecular nucleophilic substitution (S2) and proton abstraction, our quasi-classical trajectory computations reveal a novel oxide ion substitution leading to the HF + CHO products. This exothermic reaction pathway occurs the CHOH⋯F deep potential well of the S2 product channel as a result of a proton abstraction from the hydroxyl group by the fluoride ion. The present detailed dynamics study of the OH + CHF reaction focusing on the surprising oxide ion substitution demonstrates how incomplete our knowledge is of fundamental chemical reactions.
对化学反应的理论研究使我们能够理解可能反应途径的动力学，并识别新的意外途径。在此，我们为OH + CHF反应开发了一个全局分析势能面（PES），以便进行高水平的动力学模拟。除了双分子亲核取代（S2）和质子抽取外，我们的准经典轨迹计算还揭示了一种导致HF + CHO产物的新型氧化物离子取代。由于氟离子从羟基抽取质子，这种放热反应途径发生在S2产物通道的CHOH⋯F深势阱中。目前对OH + CHF反应的详细动力学研究聚焦于令人惊讶的氧化物离子取代，这表明我们对基本化学反应的了解是多么不完整。
