Gas phase electronic spectra of two C5H5 radical isomers have been observed in the 440–470 nm spectral region. The technique was a mass selective resonant two-color two-photon ionization coupled to a supersonic plasma source. Structures, relative energies and vertical electronic transition energies of six isomers of C5H5 have been calculated. Based on an analysis of the rotational profiles of the observed bands and theoretical calculations, the spectra are assigned as the Ã
2A″
←
2A″ electronic transition of isomer 1 and Ã
2A2
←
2B1 of 6 with origin band at 461.8 nm and 456.1 nm, respectively. Isomer 1, 1,3-vinylpropargyl, has Cs symmetry, while 6, a planar zig-zig chain with one hydrogen on each carbon, has C2v symmetry.
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