GamSn clusters were generated by laser ablation of a solid sample of Ga2S3. The resulting molecules were analyzed in a time-of-flight mass spectrometer. In addition to atomic species, the spectra exhibited evidence for the existence of Ga2S3+, Ga2S4+, Ga4S5+, and Ga4S6+ clusters. The potential neutral and cationic structures of the observed GamSn clusters were computationally investigated using a density-functional approach. Reference is made to the kinetic pathways required for production of clusters from the starting point of the stoichiometric molecule or molecular ion. Cluster atomization enthalpies are compared with bulk values from the literature. (C) 2009 Elsevier Ltd. All rights reserved.