Photodissociation of ICN at the liquid/vapor interface of chloroform

The photodissociation of ICN initially adsorbed at the liquid/vapor interfa ce of chloroform is studied using classical molecular dynamics computer sim ulations. The photodissociation and subsequent geminate recombination on th e ground state of ICN is compared with the same reaction in the bulk liquid . We find that the probability for cage escape at the interface is signific antly enhanced due to the possibility that one or both of the photodissocia tion fragments desorb into the gas phase. The desorption probability is sen sitive to the initial location and orientation of the ICN. An examination o f the energy disposal into these fragments provides additional information about the competition between geminate recombination and cage escape at the interface. (C) 2001 American Institute of Physics.