Abstract

The effects of collisional quenching on photofragment emission (PFE) detection of vapor-phase HgCl2 in combustion flue gas constituents are investigated. Exciting HgCl2 via the 1Πu11Σg+1 transition, time-resolved measurements of emission from the Hg(63P1) daughter in buffer-gas mixtures of N2, O2, and CO2 indicate that the fragmentation pathway passes through a long-lived intermediate species, which we assign to Hg(63P2). Total quenching rate coefficients of Hg(63P1) by N2, O2, and CO2 are consistent with values reported in the literature. In addition, total quenching rate coefficients for the intermediate Hg(63P2) state are determined to be 1.72(±0.08)×1010cm3molecule1s1 and 2.90(±0.37)×1010cm3molecule1s1 for N2 and O2, respectively. An analysis of the impact of the collisionally dependent energy-transfer process that precedes the formation of Hg(63P1) on the use of PFE to measure HgCl2 concentration is presented.

© 2008 Optical Society of America

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