Decay kinetics of NCl(b 1Σ+, v′)

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Abstract
Measurements have been made of the time decay of NCl(b 1Σ+,v′) generated by the laser photolysis (193 nm) of ClN3 diluted in helium. Rate constants for collisional quenching of the v′ = 0 level of the b 1Σ+ state are 47.7±1.3(ClN3), 0.54±0.25 (Cl2), 7.1±0.6 (F2), 38±3 (ClF), 7.4±0.3 (H2), 59±3 (HF), 33±3 (HCl), and 1.71±0.06 (CO2) in units of 103 s−1 Torr−1. These results are interpreted in terms of possible reactive and energy transfer mechanisms for electronic quenching. With the exception of ClN3, quenching within the vibrational manifold of the b 1Σ+ state is faster than electronic quenching for each of the chaperone gases tested. Analysis of the b 1Σ+ decay rate for quenching by ClN3 indicates that 13±2% of the vibrational energy contained in NCl(b 1Σ+) is utilized in enhancing the rate of the quenching process.