Adiabatic and nonadiabatic dissociation of ethyl radical.
Direct ab initio molecular dynamics using the trajectory surface hopping method with Tully's fewest switches simulates the photodissociation dynamics of ethyl radical, C(2)H(5), following electronic excitation to the A-state. Nonadiabatic dissociation dominates and produces ground state ethylene and fast hydrogen atoms with an anisotropic angular distribution. Surface hopping also generates hot ground state ethyl radicals followed ultimately by unimolecular dissociation to C(2)H(4)+H. The calculated excited state lifetime and the product recoil energy distribution obtained from an ensemble of trajectories are consistent with previous experiments and suggest that a strictly nonadiabatic mechanism can account for nonradiative decay. This process is in competition with adiabatic dissociation producing electronically excited state ethylene and H, a dissociation channel that has not yet been experimentally observed. The branching ratio between adiabatic and nonadiabatic dissociation pathways depends sensitively on the quality of the potential energy surfaces. At the multireference configuration interaction with singles and doubles level of theory, 15% of all trajectories dissociate adiabatically.
Hostettler
Jonas M
JM
Laboratorium fur Organische Chemie, ETH Zurich, Wolfgang-Pauli-Strasse 10, CH-8093 Zurich, Switzerland.
Bach
Andreas
A
Chen
Peter
P