Vibrational spectra of small silicon monoxide cluster cations measured by infrared multiple photon dissociation spectroscopy

The first gas-phase infrared spectra of silicon monoxide cations (SiO)(n)(+), n = 3-5, using multiple photon dissociation in the 550-1250 cm(-1) frequency range, are reported. All clusters studied here fragment via loss of a neutral SiO unit. The experimental spectra are compared to simulated linear absorption spectra from calculated low energy isomers for each cluster. This analysis indicates that a "ring'' isomer is the primary contributor to the (SiO)(3)(+) spectrum, that the (SiO)(4)(+) spectrum results from two close-lying bicyclic ring isomers, and that the (SiO)(5)(+) spectrum is from a bicyclic ring with a central, fourfold-coordinated Si atom. Experiment and theory indicate that the energies and energetic orderings of (SiO)(n)(+) isomers differ from those for neutral (SiO)(n) clusters.