Shattering of SiMe3+ during surface-induced dissociation

We provide experimental evidence that upon hyperthermal impact of Si(CD3)(3)(+) ions with an organic surface, a portion of the ions undergo dissociation while still in contact with the surface. We use a tandem configuration of quadrupole mass spectrometers along with an energy analyzer to measure the kinetic energy distributions of the fragments that form as a result of the surface scattering of 25 eV Si(CD3)(3)(+). These distributions are different for scattering from a clean Au(111) surface versus scattering from an organic surface composed of a self-assembled monolayer of hexanethiolate on Au(111). Parent and fragment ions recoil from the clean Au(111) surface with the same velocity, as is expected for fragmentation away from the surface. However, the same scattering products recoil from the organic surface with different velocities but similar energies, suggesting that the fragmentation dynamics are modified by surface interactions. We perform molecular dynamics simulations which predict residence times of similar to 210 fs at the organic surface and similar to 20 fs at the Au surface. The simulations also predict that 13% and 31% of the ions fragment within 1.1 ps of surface impact at the organic and Au surfaces, respectively. Thus, the experimental observation of dissociation at only the organic surface results from its longer ion-surface interaction time. The fragmentation time scale predicted by Rice-Ramsperger-Kassel-Marcus calculations is yet longer, suggesting that at least a portion of the surface-induced dissociation of Si(CD3): may occur via a nonstatistical mechanism. Our interpretation draws heavily from an analogous "shattering" mechanism previously proposed for cluster-surface scattering [E. Hendell, U. Even, T. Raz, and R. D. Levine, Phys. Rev. Lett. 75, 2670 (1995)]. (C) 1998 American Institute of Physics. [S0021-9606(98)70148-5].