Lifetimes and quenching of B 2Σ+ PO by atmospheric gases

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Abstract
Pulsed laser excited fluorescence in the B 2Σ+ ← X 2π system of gas phase PO was used to measure the lifetime for v′=0 of the B state. Rotationally resolved measurements for a few selected J′ levels, at Ar or He carrier gas pressures of ∼2 Torr, reveal no dependence of the lifetime on the rotational level excited. Earlier measurements of relative fluorescence intensities in the v′=0 vibrational progression were reinterpreted to extract the dependence of the electronic transition moment on internuclear distance. Using this transition moment, no lifetime dependence on rotational level is to be expected, even at low pressures. Rate constants for quenching of the B state PO by N2, O2, CO2, and H2O, and upper limits thereof for He and Ar are reported. O2 was found to react with ground state PO. A crude measurement of the rate constant was performed. The result is compared to two other known measurements. The rate constant is in excellent agreement with the previous measurement, but in poor agreement with that of a concurrent study. Further work is required to determine the reason for the discrepancy. A cathode ray–vidicon type waveform digitizer was found to lend itself readily to the lifetime measurements, wherein a low repetition rate laser was used. Unfortunately, it was discovered that small nonlinearities (∼1% of full scale) in the digitizer response have a marked effect on the fits to the exponential lifetime decays and, especially, the quenching rate constants. We believe this problem is not commonly recognized. A simple method for calibration of this type of digitizer and removal of these effects is presented.