Photodissociation of Arn+ cluster ions: Kinetic energy distributions of neutral fragments

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Abstract
The time-of-flight (TOF) spectra of fragments produced in the photodissociation of Arn+ (3≤n≤24) were measured at 532 nm. Analysis of these TOF spectra provides quantitative information on the kinetic energy distributions of the neutral Ar fragments. For Arn+ with n≤14, two types of Ar fragments were distinguished according to the kinetic energy release. One having a sizable amount of kinetic energy is ascribed to the fragments directly produced via the dissociation of the chromophoric core in the cluster ions. The other carrying a smaller amount of kinetic energy can be described by ‘‘evaporation’’ of solvent atoms in Arn+. The average translational energies of the ‘‘fast’’ and the ‘‘slow’’ fragments were estimated to be 0.35–0.38 and 0.07–0.1 eV, respectively, for n=7–11. The angular distribution of the fast fragments exhibits a preferential anisotropy with 1.5≲β≲2 along the direction of the polarization vector of the excitation laser, while an almost isotropic distribution was observed for the slow fragments. A possible photodissociation mechanism was proposed based on the theoretically predicted geometries of Arn+. In the TOF spectra for the larger Arn+ with 14≤n≤24, no indication was obtained for the production of the fast fragments. The average kinetic energy of the ejected neutral atoms is ∼0.05 eV at n=24. This finding indicates that the direct core dissociation no longer takes place in the larger Arn+ clusters, suggesting that the photophysical properties of Arn+ (n≥14) differ from those of the smaller cluster ions.