Ring-polymer molecular dynamical calculations for the F plus HCl -> HF plus Cl reaction on the ground 1(2)A ' potential energy surface
Ring-polymer molecular dynamical calculations for the F plus HCl -> HF plus Cl reaction on the ground 1(2)A ' potential energy surface
复制标题
DOI：
10.1039/c6cp03306g
复制
发表时间：
2016
影响因子：
3.3
通讯作者：
Li Jun
中科院分区：
文献类型：
--
作者：
Bai Mengna;Lu D;an;Li Yongle;Li Jun
采用新近发展起来的环状高分子分子动力学（RPMD）方法，对F + HCl → HF + Cl在基态势能面上的反应动力学进行了理论研究.首先，通过置换不变多项式神经网络（PIP-NN）方法，基于在来自最新和最准确的Deskevich-Hayes-Takahashi-斯科杰-Nesstrike（DHTSN）PES（J. Chem. Phys.， 2006，124，224303）。仅用521个参数就实现了出色的拟合性能。PIP-NN PES比DHTSN PES快11倍。此外，还得到了PIP-NN PES对原子坐标的一阶解析导数。计算了PIP-NN PES上的RPMD速率系数，并与现有的理论和实验结果进行了比较。结果表明，在DHTSN PES上，由于高估了反应势垒，实验速率系数明显大于理论结果。我们的结论是，一个可靠的PES这个重要的重-轻-重反应是非常可取的。
The reaction kinetics of the heavy-light-heavy abstraction reaction F + HCl → HF + Cl on the ground electronic state potential energy surface (PES) is investigated theoretically by a recently developed ring polymer molecular dynamics (RPMD) approach. First, a new PES is developed by the permutation invariant polynomial neural network (PIP-NN) approach based on 30 620 points sampled over a large configuration space from the latest and most accurate Deskevich−Hayes−Takahashi−Skodje−Nesbitt (DHTSN) PES (J. Chem. Phys., 2006, 124, 224303). Excellent fitting performance was achieved with only 521 parameters. The PIP-NN PES is 11 times faster than the DHTSN PES. Besides, the first analytical derivatives with respect to the coordinates of the atoms have been obtained for the PIP-NN PES. The RPMD rate coefficients on the PIP-NN PES are calculated and compared with available theoretical and experimental results. It is found that the experimental rate coefficients are significantly larger than the theoretical results on the DHTSN PES, due to its overestimated reaction barrier. We conclude that a reliable PES for this important heavy-light-heavy reaction is highly desirable.