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Infrared spectroscopy of the cluster ions H<sup> + </sup><sub>3</sub>·(H2)n

J. Chem. Phys. 88, 79 (1988); doi:10.1063/1.454488

Issue Date: 1 January 1988

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M. Okumura, L. I. Yeh, and Y. T. Lee
Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory and Department of Chemistry, University of California, Berkeley, California 94720
The vibrational spectra of the clusters H<sup> + </sup><sub>3</sub>(H2)n were observed near 4000 cm−1 by vibrational predissociation spectroscopy. Spectra of mass-selected clusters were obtained by trapping the ions in a radio frequency ion trap, exciting vibrational transitions of the cluster ions to predissociating levels, and detecting the fragment ions with a mass spectrometer. Low resolution bands of the solvent H2 stretches were observed for the clusters of one to six H2 coordinated to an H<sup> + </sup><sub>3</sub> ion. The red shift of these vibrations relative to the monomer H2 frequency supported the model of H<sup> + </sup><sub>9</sub> as an H<sup> + </sup><sub>3</sub> with a complete inner solvation shell of three H2, one bound to each corner of the ion. Two additional bands of H<sup> + </sup><sub>5</sub> were observed, one assigned as the H<sup> + </sup><sub>3</sub> symmetric stretch, and the other as a combination or overtone band. High-resolution scans (0.5 and 0.08 cm−1) of H<sup> + </sup><sub>n</sub>, n=5, 7, and 9 yielded no observable rotational structure, a result of either spectral congestion or rapid cluster dissociation. The band contour of the H<sup> + </sup><sub>5</sub> band changed upon cooling the internal degrees of freedom, but the peaks remained featureless. The observed frequencies of H<sup> + </sup><sub>7</sub> and H<sup> + </sup><sub>9</sub> agreed well with ab initio predictions, but those of H<sup> + </sup><sub>5</sub> did not. This deviation is discussed in terms of the large expected anharmonicity of the proton bound dimer H<sup> + </sup><sub>5</sub>. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 26 August 1987; accepted 16 September 1987
Permalink: http://link.aip.org/link/?JCPSA6/88/79/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.+d
    Studies of special atoms and molecules Atomic and molecular clusters
  • 33.20.Ea
    Molecular spectra and interactions of molecules with photons Molecular spectra, grouped by wavelength ranges Infrared spectra
  • 33.80.Gj
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Diffuse spectra; predissociation, photodissociation
  • YEAR: 1988

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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