Model-free determination of dissociation energies of polyatomic systems - art. no. 013401

We describe and apply a new procedure that allows a direct determination of dissociation energies of polyatomic systems (clusters, fullerenes, polymer s, and other molecules) without any modeling of the systems under investiga tion. As an example, we have determined the dissociation energies of a seri es of gold clusters Au-n(+). A comparison with values obtained from statist ical models of unimolecular dissociation shows that these models significan tly fail to describe the data. In contrast, the new method yields values wh ich are an order of magnitude more accurate, thus allowing one to experimen tally set benchmarks for any theory which attempts to describe activated pr ocesses.