Fragmentation of molecules sliding along surfaces in the speed range above thermal and below Bohr velocity.

A theoretical model and experimental time-of-flight mass spectrometric data for the fragmentation of molecules grazing along surfaces at velocities v = 10(5)-10(6) cm/s are presented. The effect of enhanced surface-induced dissociation at grazing incidence (GI-SID) is shown for hexadecylpyridine ions. The velocity dependence of the GI-SID fragmentation probability is studied in experiments with adduct ions of cyclodextrin derivatives. Surfaces used in the various collision experiments are aluminum oxide, gold, and a liquid film of perfluorinated polyether. In the theoretical model of the GI-SID effect we consider polyatomic molecules with substructures consisting of chains of identical biatomic dipoles. Because of the interaction with the periodic Coulomb field of the surface, collective vibrational excitations (excimols) are induced in these chains. Energy accumulation of several excimols and a subsequent energy transfer to a trap bond can induce its dissociation. An analytical expression for the velocity dependent GI-SID fragmentation probability is given, which is in good agreement with the experimental data.