| Abstract
| - The laser fluorescence excitation spectrum of the jet-cooled PO2 radical has been recorded in the wavelengthrange 325−284 nm. This work extends previous flash photolysis and laser fluorescence studies of the UVelectronic transition in PO2. Resolved emission spectra were recorded for excitation of a number of bands.The previous vibrational analyses of both the absorption and emission spectra were extended. The rotationalstructure of the bands was investigated and found to be very complicated, defying an analysis. The radiativedecays of the excited vibronic levels were found to be nonexponential but could be fitted to a double exponentialform. The lifetimes were found to be much shorter than those observed in a discharge-flow system by Hamilton[J. Chem. Phys.1987, 86, 33]. The inferred dependence of the lifetime upon the degree of rotational excitationand the complicated rotational structure of the bands suggest that there is significant electronic state mixing,as in the isovalent NO2 molecule.
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