A simple picture for the rotational enhancement of the rate for the F + HCl --> HF + Cl reaction: a dynamical study using a new ab initio potential energy surface.
Quantum scattering calculations for the reaction F + HCl --> HF + Cl are performed on a new ground-state ab initio potential energy surface. The reagent rotation is found to have a dramatic effect on the reaction probability. Furthermore, the exit channel rotational thresholds leave a strong imprint on the reaction probabilities and even on the cumulative reaction probability. A very simple vibrationally adiabatic model is shown to account for most aspects of the reaction dynamics. In this model, the fast vibrational motion is adiabatically eliminated leaving the key reaction dynamics represented by a reduced atom + rotor collision. The shape of the adiabatic potential surface immediately yields to a simple and intuitive interpretation for the rotational enhancement of the rate. The rotational enhancement is shown to be an effect of the entrance channel dynamics of the atom-rotor problem.
Hayes
Michael Y
MY
Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Deskevich
Michael P
MP
Nesbitt
David J
DJ
Takahashi
Kaito
K
Skodje
Rex T
RT