title: Mode-Specific SN2 Reaction Dynamics.
abstract: Despite its importance in chemistry, the microscopic dynamics of bimolecular nucleophilic substitution (SN2) reactions is still not completely elucidated. In this publication, the dynamics of a prototypical SN2 reaction (F(-) + CH3Cl → CH3F + Cl(-)) is investigated using a high-dimensional quantum mechanical model on an accurate potential energy surface (PES) and further analyzed by quasi-classical trajectories on the same PES. While the indirect mechanism dominates at low collision energies, the direct mechanism makes a significant contribution. The reactivity is found to depend on the specific reactant vibrational mode excitation. The mode specificity, which is more prevalent in the direct reaction, is rationalized by a transition-state-based model.
authors: Key Laboratory of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, China.|School of Chemical and Environmental Engineering, Hubei University for Nationalities , Enshi 445000, China.
authors: Yan
authors: Y
authors: Wang
authors: Key Laboratory of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, China.
authors: Hongwei
authors: H
authors: Song
authors: Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged , Rerrich Béla tér 1, Szeged H-6720, Hungary.
authors: István
authors: I
authors: Szabó
authors: Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged , Rerrich Béla tér 1, Szeged H-6720, Hungary.
authors: Gábor
authors: G
authors: Czakó
authors: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors: Hua
authors: H
authors: Guo
authors: Key Laboratory of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences , Wuhan 430071, China.
authors: Minghui
authors: M
authors: Yang