Energy partitioning during the exit channel motion for CH2OH+->CHO++H-2

Abstract

The exit channel dynamics of the four-centered elimination CH2OH+ --> CHO+ + H-2 is investigated by a classical trajectory calculation on the analytic potential energy surface reported previously (J. Chem. Phys. 104 (1996) 4517). The rotational and relative translational energies of the two separating moieties and the total vibrational energy are calculated as a function of the distance between their centers of mass. Rotational and vibrational energies are found to be determined shortly after the system leaves the transition state. Thereafter, the remainder of the reverse barrier is mostly converted to the relative translational energy. Hence, a shift technique may be used to estimate the kinetic energy release distribution for the products from the translational energy distribution obtained from the middle of the exit channel motion.