A quantum mechanical insight into SN2 reactions: Semiclassical initial value representation calculations of vibrational features of the Cl-⋯CH3Cl pre-reaction complex with the VENUS suite of codes.

摘要: The role of vibrational excitation reactants in driving reactions involving polyatomic species has been often studied by means classical or quasi-classical trajectory simulations. We propose a different approach based on investigation features the Cl-⋯CH3Cl pre-reaction complex for Cl- + CH3Cl SN2 reaction. present power spectra and frequency estimates title calculated at level classical, semiclassical, second-order perturbation theory pre-existing analytical potential energy surface. main goals paper are study anharmonic effects understanding couplings that permit transfer between collisional kinetic internal vibrations reactants. provide both quantum pictures intermode show mechanism is favored coupling C-Cl bend projectile with CH3 rocking motion target molecule. also illustrate how routines needed semiclassical spectroscopy simulations can be interfaced user-friendly way to molecular dynamics software. In particular, we an implementation into VENUS suite codes, thus providing useful computational tool users who not experts dynamics.