Mazo-Sevillano Pablo Del, Aguado Alfredo, Roncero Octavio
Unidad Asociada UAM-CSIC, Departamento de Química Física Aplicada, Facultad de Ciencias M-14, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Instituto de Física Fundamental (IFF-CSIC), CSIC, Serrano 123, 28006 Madrid, Spain.
J Chem Phys. 2021 Mar 7;154(9):094305. doi: 10.1063/5.0044009.
A new potential energy surface (PES) and dynamical study of the reactive process of HCO + OH toward the formation of HCO + HO and HCOOH + H are presented. In this work, a source of spurious long range interactions in symmetry adapted neural network (NN) schemes is identified, which prevents their direct application for low temperature dynamical studies. For this reason, a partition of the PES into a diabatic matrix plus a NN many-body term has been used, fitted with a novel artificial neural network scheme that prevents spurious asymptotic interactions. Quasi-classical trajectory (QCT) and ring polymer molecular dynamics (RPMD) studies have been carried on this PES to evaluate the rate constant temperature dependence for the different reactive processes, showing good agreement with the available experimental data. Of special interest is the analysis of the previously identified trapping mechanism in the RPMD study, which can be attributed to spurious resonances associated with excitations of the normal modes of the ring polymer.
本文给出了关于HCO + OH反应生成HCO + HO和HCOOH + H的新势能面（PES）及动力学研究。在这项工作中，识别出了对称适配神经网络（NN）方案中虚假长程相互作用的一个来源，这阻碍了它们直接用于低温动力学研究。因此，已将PES划分为一个非绝热矩阵加上一个NN多体项，并采用一种新颖的人工神经网络方案进行拟合，该方案可防止虚假渐近相互作用。已在该PES上进行了准经典轨迹（QCT）和环聚合物分子动力学（RPMD）研究，以评估不同反应过程的速率常数对温度的依赖性，结果与现有实验数据吻合良好。特别值得关注的是对RPMD研究中先前确定的俘获机制的分析，这可归因于与环聚合物正常模式激发相关的虚假共振。
