Cluster-Induced Desorption/Ionization of Polystyrene: Desorption Mechanism and Effect of Polymer Chain Length on Desorption Probability

Soft cluster-induced desorption/ionization of polystyrene oligomers was investigated with respect to application in mass spectrometry. Clear peak progressions corresponding to intact polystyrene molecules were observed in the mass spectra, and no fragmentation was detected; efficient desorption was deduced from quartz crystal microbalance measurements. Molecular dynamics (MD) simulations of the process revealed that even in the case of the nonpolar polystyrene molecules cluster-induced desorption proceeds via dissolvation in the polar clusters. Experimentally, a significantly lower desorption efficiency was observed for polystyrene molecules with larger chain length. Taking into account MD simulations and further experiments with mixed samples consisting of long- and short-chain polystyrene oligomers, the reduced desorption efficiency for longer chain polystyrene molecules was attributed to a stronger entanglement of the larger polystyrene molecules.