Cluster-induced desorption investigated by means of molecular dynamics simulations-Microsolvation in clusters of polar and non-polar constituents.

Abstract

The desorption of surface-adsorbed molecules induced by cluster-surface collisions of neutral molecular clusters, in particular, SO2 clusters, was investigated by means of molecular dynamics simulations. The desorption efficiency was found to be in general much higher for clusters of polar molecules when compared to nonpolar cluster constituents, for both nonpolar and polar adsorbates. In all cases, desorption is shown to proceed via dissolvation of the analyte in the cluster. In systems with nonpolar cluster constituents, the process is mainly driven by the increase in the entropy of the dissolved analyte in a larger cluster fragment. The latter process is enhanced by polar cluster constituents since the respective clusters show lower fragmentation at comparable kinetic energy and thus provide in average larger cluster fragments for the analytes to be dissolved in. In systems with clusters of polar constituents and polar adsorbates, the process is most efficient due to the additional energetic stabilization of the desorbed molecule in the solvation shell formed in the cluster fragment.