Recoil energy distributions for dissociation of the van der Waals molecule p-difluorobenzene-Ar with 450-3000 cm-1 excess energy -: art. no. 104305

Velocity map imaging has been used to measure the distributions of translational energy released in the dissociation of p-difluorobenzene-Ar van der Waals complexes from the (5(1)) over bar, (3(1)) over bar, (5(2)) over bar, (3(1)5(1)) over bar, (5(3)) over bar, (3(2)) over bar states. These states span 818-3317 cm(-1) of vibrational energy and correspond to a range of energies above dissociation of 451-2950 cm(-1). The translational energy release (recoil energy) distributions are remarkably similar, peaking at very low energy (10-20 cm(-1)) and decaying in an exponential fashion to approach zero near 300 cm(-1). The average translational energy released is small, shows no dependence on the initial vibrational energy, and spans the range 58-72 cm(-1) for the vibrational levels probed. The average value for the seven levels studied is 63 cm(-1). The low fraction of transfer to translation is qualitatively in accord with Ewing's momentum gap model [G. E. Ewing, Faraday Discuss. 73, 325 (1982)]. No evidence is found in the distributions for a high energy tail, although it is likely that the experiment is not sufficiently sensitive to detect a low fraction of transfer at high translational energies. The average translational energy released is lower than has been seen in comparable systems dissociating from triplet and cation states.