Abstract
The Ca+–acetylene complex is produced in a molecular beam and studied with mass-selected resonance enhanced photodissociation spectroscopy (REPD). A spectrum with sharp vibrational and rotational structure is measured near the Ca+(2P←2S) transition. Ca+–acetylene has a π-complex structure with a ground state vibrational frequency (Ca+–C2H2 stretch) of ΔG1/2″=169 cm−1 and a dissociation energy of D0″=18.6±5.0 kcal/mol. Isotopic studies performed show that Ca+–C2D2 has a ground state vibrational frequency (Ca+–C2H2 stretch) of ΔG1/2″=167 cm−1. Excited state vibrational activity is observed in the metal-ligand stretch, the C–C and C–H stretches and the cis bend. The C2v symmetry of the complex is confirmed with rotationally resolved spectra for both isotopomers, which yield a Ca+–C2H2 bond distance of r0″=2.80±0.20 Å.
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