Dynamics of unimolecular dissociation of sodium cluster ions

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Abstract
We investigate the unimolecular dissociation dynamics of energy‐rich sodium cluster ions, Na+n (5≤n≤40) by measuring the time evolution of their sequential monomer or dimer evaporative cooling. The experimental technique, tandem time‐of‐flight mass spectroscopy, measures the relative rate of competing dissociation channels from metastable ion clusters selected during an initial sampling time interval immediately following the creation of the ion cluster ensemble. Pulsed laser UV photoionization converts the distribution of neutral clusters emerging from a free‐jet expansion to the distribution of ion clusters from which the initial selection takes place. For the smaller clusters, 3≤n≤14, we compare the measured dissociation rates with those calculated from a modified version of the RRK theory of unimolecular dissociation. In applying the theory we use monomer and dimer binding energies determined from theoretical calculation. For larger clusters, 15≤n≤40, the binding energies are not known, and we invert the calculation, using measured dissociation fractions, to determine the binding energies of the cluster ions.