A kinetic study of the mercury sensitized luminescence of H2O and NH3

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Abstract
The transient species formed from the reactions of H2O and NH3 with excited Hg(6 3P0) atoms were studied by phase‐sensitive modulation spectroscopy. In the Hg/NH3 system, the (Hg⋅NH3) * exciplex was observed in emission, and its lifetime was found to be 1.7±0.1×10−6 sec; the third body stabilized reaction of NH3 with Hg(6 3P0) was found to proceed with a rate constant of k5b=2.2±0.2×10−31 (cm6/molecule2 sec) for M=N2. In the Hg/H2O system the (Hg⋅H2O) * exciplex was observed in emission and its lifetime found to be ? 3.3×10−8 sec; and the quenching of Hg(6 3P0) by water was found to have a rate constant of k4a + k4b[M] =9.4±0.5×10−15 (cm3/molecule sec) when M=1 atmosphere of N2. In the Hg/H2O system the OH radical was observed both in emission and absorption, and HgH was observed in absorption. Both of these species were shown to be formed by the nonradiative dissociation of the (Hg⋅H2O) * exciplex.