Journal of the Chemical Society - Faraday Transactions p. 2979 - 2988 (1995)
Update date:2022-08-16
Topics:
Zhao, Yao
Setser, D. W.
NCl(b1Σ+), PCl(b1Σ+) and PBr(b1Σ+) molecules have been generated in a flow reactor by passing dilute flows of NFCl2, PCl3 and PBr3 in He through a dc discharge, and the total rate constants for quenching of NCl(b1Σ+) and PCl(b1Σ+) by several diatomic and small polyatomic molecules have been measured at 300 K.Except for O2, NO2 and molecular halogenes, the rate constants are in the 1E-13 - 1E-14 cm3 molecule-1 s-1 range.The dependence of the rate constants on the properties of the reagent suggests that the dominant quenching mechanism for PCl(b) and NCl(b) is electronic-to-vibrational (E-V) energy transfer with the a1Δ state as the product, just as for the reactions of NF(b1Σ+) and PF(b1Σ+).The rate constants for quenching of NCl(b1Σ+) and PCl(b1Σ+) by O2 are 1.0E-12 and 3 molecule-1 s-1, respectively, and are in accord with an electronic-to-electronic (E-E) energy transfer with the final states being O2(b1Σ+) + NCl(X3Σ+) or PCl(X3Σ-).Formation of PBr(b1Σ+) from the PCl(b1Σ+) + Br2 reaction was observed, and quenching of PCl(b1Σ+) by F2, Cl2 and Br2 proceeds by a chemical mechanism with rate constants of 2.3E-12, 0.79E-12 and 16E-12 cm3 molecule-1 a-1, respectively.The radiative lifetimes for NCl(b1Σ+), PCl(b1Σ+) and PBr(b1Σ+) are 2.0 +/- 0.4, 4.9 +/- 0.8 and 0.8 +/- 0.2 ms, respectively, as determined from the decay of the respective b1Σ+ -> X1Σ- emission intensities along the flow reactor.
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