Mode-Specific S(N)2 Reaction Dynamics

Despite its importance in chemistry, the microscopic dynamics of bimolecular nucleophilic substitution (S(N)2) reactions is still not completely elucidated. In this publication, the dynamics of a prototypical S(N)2 reaction (F- + CH3CL -> CH3F + Cl-) is investigated using a high-dimensional quant...

Teljes leírás

Elmentve itt :
Bibliográfiai részletek
Szerzők: Wang Yan
Song Hongwei
Szabó István
Czakó Gábor
Guo Hua
Yang Minghui
Dokumentumtípus: Cikk
Megjelent: 2016
Sorozat:JOURNAL OF PHYSICAL CHEMISTRY LETTERS 7 No. 17
doi:10.1021/acs.jpclett.6b01457

mtmt:3119119
Online Access:http://publicatio.bibl.u-szeged.hu/17922
Leíró adatok
Tartalmi kivonat:Despite its importance in chemistry, the microscopic dynamics of bimolecular nucleophilic substitution (S(N)2) reactions is still not completely elucidated. In this publication, the dynamics of a prototypical S(N)2 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.
Terjedelem/Fizikai jellemzők:3322-3327
ISSN:1948-7185