Photodissociation spectroscopy of Ca+(C2H4)

We have studied Ca+(C2H4) by photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer over the spectral range 440–790 nm. Ca+ is the only photofragment observed. We find four absorption bands of the complex and assign them to metal-centered transitions correlating with excitat...

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Veröffentlicht in:The Journal of chemical physics 2000-04, Vol.112 (15), p.6583-6589
Hauptverfasser: Holmes, J. H., Kleiber, P. D., Olsgaard, D. A., Yang, K.-H.
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Sprache:eng
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Zusammenfassung:We have studied Ca+(C2H4) by photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer over the spectral range 440–790 nm. Ca+ is the only photofragment observed. We find four absorption bands of the complex and assign them to metal-centered transitions correlating with excitation of Ca+(3d and 4p). Spectral assignment is supported by ab initio electronic structure calculations of the complex and isotope substitution experiments. Calculations find a weakly bound ground state equilibrium structure with C2V π-bonding geometry and a dissociation energy of De″=0.506 eV. Theoretical and experimental results show the 4pπ(2 2B2 & 2 2B1) excited states to be relatively weakly bound at long range. Spectral analysis gives vibrational constants for the Ca+--C2H4 intermolecular a1-stretch in the 1 2A1, 2 2B1, and 2 2B2 states, and for the CH2–CH2 a1-wag and the HCH a1-bend in 2 2B2. The results offer an interesting comparison with previous studies of similar weakly bound bimolecular complexes of light metal ions with alkene or alkane hydrocarbons.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.481231