Nonadiabatic photodissociation dynamics in (HI)(2) induced by intracluster collisions

摘要

The sequential photodissociation dynamics of (HI)(2) is studied by means of a nonadiabatic wave packet treatment starting from the I*-HI complex. The model reproduces the main experimental findings for photolysis with 266 nm radiation. The results confirm that some of the H atoms dissociated from the I*-HI complex deactivate the I* atom through a H/I-* intracluster collision which induces an I*-> I electronically nonadiabatic transition. As a consequence, these H fragments become very fast by acquiring nearly all the I* excitation energy, equivalent to the I*/I spin-orbit splitting. A most interesting result is the high production of bound I-2 fragments in highly excited rovibrational states in the photolysis, indicating that the H dissociation is mainly direct. (c) 2007 American Institute of Physics.