Chen Qixin, Hu Xixi, Guo Hua, Xie Daiqian
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Kuang Yaming Honors School, Nanjing University, Nanjing 210023, China.
Phys Chem Chem Phys. 2021 Feb 12;23(5):3300-3310. doi: 10.1039/d0cp05771a.
Thermal rate coefficients and kinetic isotope effects have been calculated for an important atmospheric reaction H/D + O3 → OH/OD + O2 based on an accurate permutation invariant polynomial-neural network potential energy surface, using ring polymer molecular dynamics (RPMD), quasi-classical trajectory (QCT) and variational transition-state theory (VTST) with multidimensional tunneling. The RPMD approach yielded results that are generally in better agreement with experimental rate coefficients than the VTST and QCT ones, especially at low temperatures, attributable to its capacity to capture quantum effects such as tunneling and zero-point energy. The theoretical results support one group of existing experiments over the other. In addition, rate coefficients for the D + O3 → OD + O2 reaction are also reported using the same methods, which will allow a stringent assessment of future experimental measurements, thus helping to reduce the uncertainty in the recommended rate coefficients of this reaction.
基于精确的置换不变多项式-神经网络势能面，利用环聚合物分子动力学（RPMD）、准经典轨迹（QCT）和包含多维隧穿的变分过渡态理论（VTST），计算了大气中一个重要反应H/D + O₃ → OH/OD + O₂的热速率系数和动力学同位素效应。RPMD方法得到的结果通常比VTST和QCT方法得到的结果与实验速率系数的吻合度更高，尤其是在低温下，这归因于其捕捉隧穿和零点能等量子效应的能力。理论结果支持了一组现有实验而不是另一组。此外，还使用相同方法报道了D + O₃ → OD + O₂反应的速率系数，这将有助于对未来的实验测量进行严格评估，从而有助于降低该反应推荐速率系数的不确定性。
