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The role of vibrational excitation of reactants in driving reactionsinvolving polyatomic species has been often studied by means of classical orquasi-classical trajectory simulations. We propose a different approach basedon investigation of vibrational features of the Cl$^-$--CH$_3$Cl pre-reactioncomplex for the Cl$^-$ + CH$_3$Cl SN$_2$ reaction. We present vibrational powerspectra and frequency estimates for the title pre-reaction complex calculatedat the level of classical, semiclassical, and second-order vibrationalperturbation theory on a pre-existing analytical potential energy surface. Themain goals of the paper are the study of anharmonic effects and understandingof vibrational couplings that permit energy transfer between the collisionalkinetic energy and the internal vibrations of the reactants. We provide bothclassical and quantum pictures of intermode couplings and show that the SN2mechanism is favored by the coupling of a C--Cl bend involving the Cl$^-$projectile with the CH$_3$ rocking motion of the target molecule. We alsoillustrate how the routines needed for semiclassical vibrational spectroscopysimulations can be interfaced in a user-friendly way to pre-existing moleculardynamics software. In particular, we present an implementation of semiclassicalspectroscopy into the VENUS suite of codes, thus providing a usefulcomputational tool for users who are not experts of semiclassical dynamics.

journal of chemical physics online/the journal of chemical physics/journal of chemical physics

A quantum mechanical insight into SN2 reactions: Semiclassical initial  value representation calculations of vibrational features of the  Cl$^-$--CH$_3$Cl pre-reaction complex with the VENUS suite of codes