首页> 美国政府科技报告 >Quenching Rate Constants for NCl(b(1) Sigma (+)) and PCl(b(1) Sigma (+)) andRadiative Lifetimes of NCl(b(1) Sigma (+)) PCl(b(1) Sigma (+))and PBr(b(1) Sigma (+))
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Quenching Rate Constants for NCl(b(1) Sigma (+)) and PCl(b(1) Sigma (+)) andRadiative Lifetimes of NCl(b(1) Sigma (+)) PCl(b(1) Sigma (+))and PBr(b(1) Sigma (+))

机译:NCl(b(1)sigma(+))和pCl(b(1)sigma(+))的猝灭速率常数和NCl(b(1)sigma(+))pCl(b(1)sigma(+)的辐射寿命))和pBr(b(1)sigma(+))

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No(bls+), PO(b1S+) and PBr(b'S+) molecules have been generated in a flow reactorby passing dilute flows of NFCl2, PC, and PBr, in He through a dc discharge, and the total rate constants for quenching of NCl(b'S+) and PCl(b1%+) by several diatomic and small polyatomic molecules have been measured at 300 K. Except for %, N% and molecular halogens, the rate constants are in the 1Oi%.1Oi4 Cm3 moIecule%L 5%L 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-vibrationa (E-v) energy transfer with the a1% state as the product, just as for the reactions of NF(b1S+) and PF(b1S+). The rate constants for quenching of NCl(b1%+) and PCl(b1E+) by O2 are 1.0 x 1012 and % 1015 cm3 molecule' %L, respectively, and are in accord with an electronic-to-electronic (E-E) energy transfer. Formation of PBr(b1S+) from the PCl(b1S+) plus Br2 reaction was observed, and quenching of PCl(b1E+) by F2, Cl2 and Br proceeds by a chemical mechanism. The radiative lifetimes for NCl(b1S+), PCl(b1S+) and PBr(b1S+) are 2.OjO.4, 4.9j0.8 and 0.810.2 ms, respectively, as determined from the decay of the respective singlet sigma b x1r emission intensities along the flow reactor.

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