Journal of Chemical Physics, Vol.112, No.24, 10831-10837, 2000
Vibrational mode and collision energy effects on proton transfer in phenol cation-methylamine collisions
Mass-analyzed threshold ionization has been used to prepare vibrationally state-selected phenol cations, that were then reacted with methylamine at collision energies ranging from 0.1 to 2 eV. Integral cross sections and product recoil velocity distributions are reported. Ab initio calculations of stationary points on the surface and RRKM (Rice-Ramsperger-Kassel-Marcus) analysis of complex lifetimes are also presented for comparison. The only reaction observed over the entire energy range is exoergic proton transfer (PT). For ground-state reactants, the PT cross section is reduced by increasing collision energy, such that the reaction efficiency declines from similar to 71% at low E-collision to similar to 50% at 2 eV. Excitation of either v(6a) or v(12) vibrations inhibits reaction over the entire collision energy range, with the effect being somewhat mode-specific and increasing with increasing E-collision. At low E-collision, both vibrational and collision energy inhibit reaction with similar efficiency. Collision energy effects diminish at high E-collision, while vibration continues to have a strong effect. Product ion velocity distributions are approximately forward-backward symmetric at E-collision less than or equal to 1 eV, but are backward peaked at high energies. Mechanistic implications of these results are discussed.