Li Lulu, Fu Bina, Yang Xueming, Zhang Dong H
Department of Chemical Physics, University of Science and Technology of China, Jinzhai Road 96, Hefei 230026, China and State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
Phys Chem Chem Phys. 2020 Apr 15;22(15):8203-8211. doi: 10.1039/d0cp00107d.
We report an accurate full-dimensional potential energy surface (PES) of the anion-molecule system OH3-. The PES was constructed by fitting 55 406 ab inito energies from the CCSD(T)/aug-cc-pVTZ level of theory with the fundamental invariant neural network (FI-NN) approach, resulting in an extremely small fitting error of 0.52 meV. Extensive quasiclassical trajectory (QCT) simulations were carried out on the PES to investigate the proton transfer dynamics (OH- + D2 → D- + HOD). The product D- translational energy distribution and angular distribution were calculated and compared with previous experimental measurements, in which reasonably good agreement has been achieved. The angular distribution at a high collision energy exhibits an exclusively forward scattering peak, indicating the direct stripping mechanism at high energies. With the decrease of the collision energy, the reaction shows a predominantly forward scattering feature, with very small sideways and backward scattering amplitudes, revealing combined mechanisms from direct abstraction with a short reaction time and a complex-forming process with a long reaction time.
我们报告了阴离子 - 分子系统OH3-的精确全维势能面（PES）。该势能面是通过使用基本不变神经网络（FI-NN）方法拟合来自CCSD(T)/aug-cc-pVTZ理论水平的55406个从头算能量构建而成的，拟合误差极小，仅为0.52毫电子伏特。在该势能面上进行了广泛的准经典轨迹（QCT）模拟，以研究质子转移动力学（OH- + D2 → D- + HOD）。计算了产物D-的平动能分布和角分布，并与先前的实验测量结果进行了比较，结果显示出合理的良好一致性。在高碰撞能量下的角分布呈现出一个完全向前散射的峰，表明在高能量下存在直接剥离机制。随着碰撞能量的降低，反应主要呈现向前散射特征，侧向和向后散射幅度非常小，这揭示了反应时间短的直接提取和反应时间长的复合物形成过程的组合机制。
