Affiliation:
1. MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged , Rerrich Béla tér 1, Szeged H-6720, Hungary
Abstract
We develop a full-dimensional analytical potential energy surface (PES) for the F− + SiH3Cl reaction using Robosurfer for automatically sampling the configuration space, the robust [CCSD-F12b + BCCD(T) − BCCD]/aug-cc-pVTZ composite level of theory for computing the energy points, and the permutationally invariant polynomial method for fitting. Evolution of the fitting error and the percentage of the unphysical trajectories are monitored as a function of the iteration steps/number of energy points and polynomial order. Quasi-classical trajectory simulations on the new PES reveal rich dynamics resulting in high-probability SN2 (SiH3F + Cl−) and proton-transfer (SiH2Cl− + HF) products as well as several lower-probability channels, such as SiH2F− + HCl, SiH2FCl + H−, SiH2 + FHCl−, SiHFCl− + H2, SiHF + H2 + Cl−, and SiH2 + HF + Cl−. The Walden-inversion and front-side-attack-retention SN2 pathways are found to be competitive, producing nearly racemic products at high collision energies. The detailed atomic-level mechanisms of the various reaction pathways and channels as well as the accuracy of the analytical PES are analyzed along representative trajectories.
Funder
National Research, Development and Innovation Office
Ministry of Innovation and Technology of Hungary
Momentum Program of the Hungarian Academy of Sciences
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy
Cited by
3 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献