We advance a theoretical model for wbrational predissociation (VP) of a linear triatomic molecular comple\ consistmg of a rare-gas atom bound to a diatomic, which rests on the decay of a bound state into a mnnïfold of coupled translational continua. We explored the dependence of the VP :ate on the molecuIar parameters of the complex, establishing .m energy gap law for VP. The effects of intercontinuum coupling on the dynamics of VP were investissted.
Intrarnolecular dynamics of van der
Waals molecules (VDWM) which were recently observed and studied [ l-81 in supersonic beams, constitute a problem of considerable current interest_ Intramolecular relaxation processes in vibrationally excited levels of the ground electronie state and in electronically-vibrationally excited states of VDWM involve the breakïng of weak chemical bonds [9], which are characterized by bond dissociation energïes of =20-200 cm-l . Recently, Kim et al. [9-1 l] have provided an interesting study of the photodissociation dynamics of Hela, Ne12 and Ar12. Such photochemical decomposition processes provide a unique example for vibrational predissociation (VP) in a new class of weakly-bound molecular complexes. In general, the distinction between VP, resulting from nuclear motion on a single multidimensional potential surface of an excited electronic state, and electronic predissociation, involving two electronïc contìgurations, is not weli defìned [ 121, and experimental evidente for VP processes is sparse [ 12 ] . It is thus not surprising that the interestïng area of VP processes was not yet explored theoretically. Rosen's work 1131 on the