Journal of Physical Chemistry A, Vol.122, No.41, 8143-8151, 2018
Mode-Specific Quasiclassical Dynamics of the F- + CH3I S(N)2 and Proton-Transfer Reactions
Mode-specific quasiclassical trajectory computations are performed for the F- + CH3I(v(k) = 0, 1) S(N)2 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 (v(3)), CH3 rocking (v(6)), CH3 umbrella (v(2)), CH3 deformation (v(5)), CH symmetric stretching (v(1)), and CH asymmetric stretching (v(4)) 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(N)2 inversion inhibition/enhancement at low/high collision energies (E-coll), whereas large decaying-with-E-coll vibrational enhancement effects for the S(N)2 retention (double inversion) and proton-transfer channels. The most efficient vibrational enhancement is found by exciting the CI stretching (high E-coll) for S(N)2 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(N)2/proton-transfer product internal energies.