Experimental Studies of Resonances in Unimolecular Decomposition

▪ Abstract In recent years we have witnessed tremendous progress in our understanding of unimolecular reactions on a fully state-resolved level. Here we describe recent state-resolved experimental studies of resonances in unimolecular reactions, focusing on the transition from isolated to overlapping resonances. Depending on the well depth and extent of intramolecular vibrational energy redistribution, the resonances can exhibit properties ranging from mode- and state-selective to statistical behavior. In the statistical limit the resonances are usually overlapped, and interference effects may become prominent. We use recent studies of HCO, HFCO, and CH 3 O to examine the transition from mode-selective to statistical behavior in the isolated regime. Experimental and theoretical studies of NO 2 , including photofragment yield spectra, fully resolved NO quantum state distributions, and decomposition rates are used to examine unimolecular decomposition in the regime of overlapping resonances.