Size-dependent H and H₂ formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations,...

Infrared spectra of the hydrated vanadium cation (V⁺(H₂O)_n; n = 3-51) were measured in the O-H stretching region employing infrared multiple photon dissociation (IRMPD) spectroscopy. Spectral fingerprints, along with size-dependent fragmentation channels, were observed and rationalized by comparing to spectra simulated using density functional theory. Photodissociation leading to water loss was found for cluster sizes n = 3-7, consistent with isomers featuring intact water ligands. Loss of molecular hydrogen was observed as a weak channel starting at n = 8, indicating the advent of inserted isomers, HVOH⁺(H₂O)_n-1. The majority of ions for n = 8, however, are composed of two-dimensional intact isomers, concordant with previous infrared studies on hydrated vanadium. A third channel, loss of atomic hydrogen, is observed weakly for n = 9-11, coinciding with the point at which the H and H₂O calculated binding energies become energetically competitive for intact isomers. A clear and sudden spectral pattern and fragmentation channel intensity at n = 12 suggest a structural change to inserted isomers. The H₂ channel intensity decreases sharply and is not observed for n = 20 and 25-51. IRMPD spectra for clusters sizes n = 15-51 are qualitatively similar indicating no significant structural changes, and are thought to be composed of inserted isomers, consistent with recent electronic spectroscopy experiments.