Papp Dóra, 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. 2020 Aug 14;153(6):064305. doi: 10.1063/5.0018894.
We report a detailed quasi-classical dynamics study on a new full-dimensional multireference spin-orbit-corrected potential energy surface (PES) for the F(P) + CH → HF + CH reaction. For the PES development, the Robosurfer program package is applied and the MRCI-F12+Q(5,3)/aug-cc-pVDZ energy points are fitted using the monomial symmetrization approach of the permutationally invariant polynomial method. Our simulations provide substantial reaction probabilities and sharply increasing cross sections with an increase in collision energy for this early- and negative-barrier reaction. A direct rebound/stripping mechanism is preferred at low/high collision energies, and the initial translational energy turns out to convert mostly into product recoil, whereas the reaction energy excites the HF vibration. Vibrational and vibrationally resolved rotational state distributions of the HF product obtained from our computations agree well with the single-collision experimental data for the v = 1, 2, and 3 states.
我们报告了一项关于F(P)+CH→HF+CH反应的新的全维多参考自旋轨道校正势能面（PES）的详细准经典动力学研究。在PES开发过程中，应用了Robosurfer程序包，并使用置换不变多项式方法的单项式对称化方法拟合了MRCI-F12+Q(5,3)/aug-cc-pVDZ能量点。对于这个早期负势垒反应，我们的模拟提供了大量的反应概率，并且随着碰撞能量的增加，截面急剧增加。在低/高碰撞能量下，直接反弹/剥离机制更受青睐，初始平动能大部分转化为产物反冲，而反应能激发HF振动。我们计算得到的HF产物的振动和振动分辨转动状态分布与v = 1、2和3态的单碰撞实验数据吻合良好。
