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...
Elmentve itt :
Szerzők: | |
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Dokumentumtípus: | Cikk |
Megjelent: |
2016
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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 |
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. |
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Terjedelem/Fizikai jellemzők: | 3322-3327 |
ISSN: | 1948-7185 |