Tasi Domonkos A, Czakó Gábor
MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary.
J Chem Phys. 2022 May 14;156(18):184306. doi: 10.1063/5.0091789.
Investigations on the dynamics of chemical reactions have been a hot topic for experimental and theoretical studies over the last few decades. Here, we carry out the first high-level dynamical characterization for the polyatom-polyatom reaction between NH and CHI. A global analytical potential energy surface is developed to describe the possible pathways with the quasi-classical trajectory method at several collision energies. In addition to S2 and proton abstraction, a significant iodine abstraction is identified, leading to the CH + [NH⋯I] products. For S2, our computations reveal an indirect character as well, promoting the formation of [CH⋯NH] complexes. Two novel dominant S2 retention pathways are uncovered induced by the rotation of the CH fragment in these latter [CH⋯NH] complexes. Moreover, these uncommon routes turn out to be the most dominant retention paths for the NH + CHI S2 reaction.
在过去几十年中，化学反应动力学的研究一直是实验和理论研究的热门话题。在此，我们对NH与CHI之间的多原子-多原子反应进行了首次高水平的动力学表征。通过开发一个全局解析势能面，利用准经典轨迹方法在几个碰撞能量下描述了可能的反应途径。除了S2和质子提取外，还发现了显著的碘提取，生成CH + [NH⋯I]产物。对于S2反应，我们的计算也揭示了其间接特征，促进了[CH⋯NH]络合物的形成。在这些[CH⋯NH]络合物中，CH片段的旋转诱导发现了两条新的主导S2保留途径。此外，这些不常见的途径成为NH + CHI S2反应中最主要的保留路径。
