Abstract
This work is concerned with evaporation from an ill-defined miscellany of isolated aggregates. The evaporative ensemble is accordingly defined and its time-dependent properties developed. Initially this is done using phenomenologically-derived expressions for rates of evaporation. They assume implicitly that the thermodynamic properties of aggregates are continuous functions of their size. Several general properties of unimolecular rate constants are then used to show how local irregularities in these properties will manifest themselves within the ensemble. In particular the Carnot-Kelvin factor is seen to be capable of magnifying the effect of small deviations to discernible magnitudes. This magnification must nevertheless be a decreasing function of time. A concomitant de-evolution of magic-number effects follows inescapably. The manifestation of local deviations in metastable abundances is also investigated, and is illustrated by reference to evaporation from ionic copper clusters.
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Research sponsored by the Office of Health and Environmental Research, U.S. Department of Energy under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc.