Analysis of borderline substitution/electron transfer pathways from direct ab initio MD simulations

Abstract

Ab initio molecular dynamics simulations were carried out for the borderline reaction pathways in the reaction of CH 2O − with CH 3Cl. The simulations reveal distinctive features of three types of mechanisms passing through the S N2-like transition state (TS): (i) a direct formation of S N2 products, (ii) a direct formation of ET products, and (iii) a two-step formation of ET products via the S N2 valley. The direct formation of the ET product through the S N2-like TS appears to be more favorable at higher temperatures. The two-step process depends on the amount of energy that goes into the C–C stretching mode.