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 |
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Hauptverfasser: | , , , |
Format: | Artikel |
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. |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/1.481231 |