[en] Retarding Field analysis ; KERD ; Dissociative photoionization ; Maximum Entropy Method (MEM) ; He(I), Ne(I), Ar(II) ; Ab initio Calculations
[en] A retarding field technique coupled with a quadrupole mass analyzer has been used to obtain the kinetic energy release distributions (KERDs) for C2H3Br+->[C2H3]++Br dissociation as a function of the internal energy. The KERDs obtained by dissociative photoionization using the He(I), Ne(I) and Ar(II) resonance lines were analyzed by the maximum entropy method and were found to be well described by introducing a single dynamical constraint, namely the relative translational momentum of the fragments. Ab initio calculations reveal the highly fluxional character of the C2H3+ ion. As the energy increases, several vibrational modes are converted in turn into large-amplitude motions. Our main result is that, upon increasing internal energy, the fraction of phase space sampled by the pair of dissociating fragments is shown to first decrease, pass through a shallow minimum around 75%, and then increase again, reaching almost 100% at high internal energies (8 eV). This behaviour at high internal energies is interpreted as resulting from the conjugated effect of intramolecular vibrational redistribution (IVR) and radiationless transitions among potential energy surfaces. Our findings are consistent with the coincidence data of Miller and Bear, reanalyzed here, and with the KERD of the metastable dissociation.