Following the photoexcitation of argon cluster ions, Ar+nfornin the range 4ndash;25, kinetic energy release measurements have been undertaken on the fragments using two quite separate techniques. For Ar+4ndash;Ar+6, fragmentionkinetic energy spectra were recorded at 532 nm in a crossed beam apparatus as a function of the angle of polarization of the laser radiation with respect to the incident ion beam. Only Ar+from Ar+4was observed to exhibit a polarization dependence together with a comparatively high kinetic energy release. The principal fragment ion Ar+2was found both to emerge with a low kinetic energy release and to display no dependence on the angle of polarization of the radiation. In a second series of experiments, mass and kinetic energy resolved cluster ions were photodissociated in the entrance to a timehyphen;ofhyphen;flight (TOF) device of variable length. The subsequent deflection of all ions allowed for time resolved measurements to be undertaken on theneutralphotofragments. Following the absorption of a photon, all cluster ions up to Ar+25were found to eject one/two neutral atoms with comparatively high kinetic energies. Any remaining internal energy appears to be dissipated through the loss of further neutral atoms with low kinetic energies. An analysis of the laser polarization dependence of these events, shows that those atoms identified as having high kinetic energies are ejected on a time scale which is short compared with the rotation period of a cluster (bartil;10 ps).These experimental observations are consistent with the results of recent molecular dynamics simulations of excited states in rare gas clusters by Landman, Jortner, and cohyphen;workers lsqb;J. Phys. Chem.91, 4890 (1987); J. Chem. Phys.88, 4273 (1988)rsqb;. Kinetic energy releases calculated from the TOF spectra exhibit marked fluctuations as a function of cluster size, with Ar+15showing a minimum and Ar+19a maximum. It is suggested that such behavior is part of a dynamic response to changes in structure as the cluster ions increase in size. A qualitative explanation is provided through the assumption that the cluster ions take the form of solvated Ar+2structures. Considerations of the energy available from the photon and the relative contribution each TOF feature makes to the total signal, places an upper limit of two as the number of high kinetic energy atoms ejected by the larger cluster ions.
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