Abstract
Cluster ions of H7(+)/D7(+) and H9(+)/D9(+) produced in a supersonic molecular beam with a pulsed discharge source are mass selected and studied with infrared laser photodissociation spectroscopy. Photodissociation occurs by the loss of H2 (D2) from each cluster, producing resonances in the 2000-4500 cm(-1) region. Vibrational patterns indicate that these ions consist of an H3(+) (D3(+)) core ion solvated by H2 (D2) molecules. There is no evidence for the shared proton structure seen previously for H5(+). The H3(+) ion core vibrational bands are weakened and broadened significantly, presumably by enhanced rates of intramolecular vibrational relaxation. Computational studies at the DFT/B3LYP or MP2 levels of theory (including scaling) are adequate to reproduce qualitative details of the vibrational spectra, but neither provides quantitative agreement with vibrational frequencies.
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