Mode-Specific Quasiclassical Dynamics of the F^– + CH₃I S_N2 and Proton-Transfer Reactions

Abstract

Mode-specific quasiclassical trajectory computations are performed for the F^- + CH₃I( v _k = 0, 1) S_N2 and proton-transfer reactions at nine different collision energies in the range of 1.0-35.3 kcal/mol using a full-dimensional high-level ab initio analytical potential energy surface with ground-state and excited CI stretching ( v₃), CH₃ rocking ( v₆), CH₃ umbrella ( v₂), CH₃ deformation ( v₅), CH symmetric stretching ( v₁), and CH asymmetric stretching ( v₄) initial vibrational modes. Millions of trajectories provide statistically definitive mode-specific cross sections, opacity functions, scattering angle distributions, and product internal energy distributions. The excitation functions reveal slight vibrational S_N2 inversion inhibition/enhancement at low/high collision energies ( E_coll), whereas large decaying-with- E_coll vibrational enhancement effects for the S_N2 retention (double inversion) and proton-transfer channels. The most efficient vibrational enhancement is found by exciting the CI stretching (high E_coll) for S_N2 inversion and the CH stretching modes (low E_coll) for double inversion and proton transfer. Mode-specific effects do not show up in the scattering angle distributions and do blue-shift the hot/cold S_N2/proton-transfer product internal energies.