Photofragment translational spectroscopy of weakly bound complexes: probing the interfragment correlated final state distributions.

The vibrational predissociation dynamics of weakly bound complexes is well known to be highly nonstatistical. In particular, the associated photofragment final state distributions are often far from statistical, consequently reflecting the nature of the dissociation process. For binary complexes consisting of two molecules, a complete description of the final state of the system must include the associated interfragment correlations, specifically between their internal states. Information of this type is imprinted in the translational energies of the fragments, which can be measured using a number of recently developed translational spectroscopy methods. These data can provide detailed insights into the nature of the bond rupture process, as well as accurate values for the dissociation energy of the complexes. The focus of the present review is on experiments that provide correlated final state distributions for weakly bound binary complexes. Where possible, comparisons with theoretical calculations are made.