Nonadiabatic dissociation dynamics of Cl⋯HD van der Waals complex initiated by electron detachment of Cl −–HD

Abstract

Nuclear dynamics following the electron detachment of the Cl −–HD anion is investigated by a time-dependent wave packet propagation approach. Photodetachment of Cl −–HD promotes it to the van der Waals well region of the reactive Cl⋯HD potential energy surface. The latter is a manifold of three electronic states coupled by the electronic and (relativistic) spin-orbit coupling. Among the three surfaces, the electronic ground one is of 2Σ 1/2 type and yields products in their electronic ground state. The remaining two, 2Π 3/2 and 2Π 1/2, on the other hand, yield products in their excited electronic states. However, these two can yield products in their electronic ground state via nonadiabatic transitions to the 2Σ 1/2 state. The channel specific, HCl + D or DCl + H or Cl + HD, dissociation probabilities on this latter state are calculated both in the uncoupled and coupled surface situations. Separate initial transitions (via, photodetachment) to the 2Σ 1/2, 2Π 3/2 and 2Π 1/2 adiabatic electronic states of Cl⋯HD are considered in order to elucidate the nonadiabatic coupling effects on this important class of chemical reactions initiated by an electron detachment.