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

• Published in: The Journal of chemical physics Vol. 126; no. 16; p. 161102
• Main Authors: López-López, S, Prosmiti, R, García-Vela, A
• Format: Journal Article
• Language: English
• Published: United States 28.04.2007
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.2731371

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 HI* 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 I2 fragments in highly excited rovibrational states in the photolysis, indicating that the H dissociation is mainly direct.