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Ionic clusters consisting of a polyatomic ion surrounded by a few 'solvent' atoms or molecules, provide a connecting link between the isolated gas phase ion and the ion solvated in a condensed medium. Analysis of the vibrational structure associated with the motion of the cluster atoms can reveal details concerning the intermolecular potential. However, for large polyatomic ions, information concerning the cluster vibrational motion has been difficult to obtain using conventional spectroscopic methods. We have developed a new combination of the previously available techniques of supersonic cooling, resonance-enhanced multi photon ionisation, timeof- flight mass spectroscopy, in concert with one-photon photodissociation spectroscopy. This new technique takes advantage of the facile predissociation of an electronically excited cluster and affords us a method of studying the previously unmeasurable vibrational structure associated with the motion of a molecular cluster ion. Using this technique we have obtained vibrationally resolved photodissociation spectra of a number of aromatic-rare gas cluster ions. Analysis of their vibrational structure permits structural details of the cluster cation to be deduced.

Spectroscopy and Structure of Aromatic?Rare Gas Cluster Ions