A global ab initio potential energy surface and dynamics of the proton-transfer reaction: OH- + D2 → HOD + D. 2020

Lulu Li, and Bina Fu, and Xueming Yang, and Dong H Zhang
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. bina@dicp.ac.cn zhangdh@dicp.ac.cn.

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.

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