Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH2O?- with CH3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the SN2-like transition state (TS): i) a direct formation of SN2 products, ii) a direct formation of ET products, and iii) a 2-step formation of ET products via the SN2 valley. The direct formation of the ET product through the SN2-like TS appears to be more favorable at higher temperatures. The 2-step process depends on the amount of energy that goes into the C-C stretching mode.
Revised: March 19, 2002 |
Published: February 19, 2002
Citation
Yamataka H., M.A. Aida, and M. Dupuis. 2002.Analysis of Borderline Substitution/Electron Transfer Pathways from Direct ab initio MD Simulations.Chemical Physics Letters 353, no. 3-4:310-316.PNNL-SA-35808.