Infrared spectra of mass-selected Al+-(CH4)n n = 1-6 clusters

B. L.J. Poad, C. D. Thompson, E. J. Bieske

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Abstract

Infrared spectra are recorded for Al+-(CH4)n n = 1-6 clusters in the CH stretch region (2800-3100 cm-1). The spectra, which are obtained by monitoring photofragmentation in a tandem mass spectrometer, are dominated by a single, narrow band corresponding to the totally symmetric C-H stretching mode of the CH4 subunits (rendered infrared active through the interaction with the Al+ cation). This band shifts progressively to higher wavenumber as the clusters becomes larger, concomitant with a weakening of the intermolecular Al+⋯CH4 bonds. Supporting ab initio calculations for the n = 1-6 clusters at the MP2/aug-cc-pVDZ level indicate that the Al+ cation is attached to each CH4 sub-unit in a face-bound η3 configuration and that when possible the methane molecules are adjacent to one another. Clusters built around an inserted [H-Al-CH3]+ core are also predicted to be stable but lie higher in energy than clusters built around an Al+ core; the latter species are the only ones observed experimentally. Crown

Original languageEnglish
Pages (from-to)176-181
Number of pages6
JournalChemical Physics
Volume346
Issue number1-3
DOIs
Publication statusPublished - 4 May 2008

Keywords

  • Aluminium cation
  • Infrared photodissociation spectroscopy
  • Metal cation cluster
  • Methane

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