Photoinduced Bond Cleavage as a Probe of Mode Specificity and Intramolecular Dynamics in Rovibrationally Excited Triatomic to 10 Atom Molecules

This chapter overviews the research on intramolecular dynamics in rovibrationally excited molecules and our work on mode- and bond-selective photodissociation in the context of the pioneering work of Moshe Shapiro on this subject. The concept of rovibrationally mediated photodissociation (VMP) is presented and its application to selective or preferential bond cleavage is discussed via presentation of some examples: first the VMP of water isotopologues, which was in the focus of this field in its early days, and then of our more recent work on larger molecules, methylamine and pyrrole, providing evidence for mode specificity in 7 and 10 atom molecules, respectively. We point out that additional work has to be carried out in larger molecules in attempt to find out what are the limits of size and conditions where nonstatistical behavior is still feasible.