Abstract
The recombination reaction H + O/sub 2/ + M ..-->.. HO/sub 2/ + M is studied by laser flash photolysis in the bath gases M = Ar, N/sub 2/, and CH/sub 4/ at pressures between 1 and 200 bar. By extrapolation of the falloff curves, a limiting high-pressure rate coefficient k/sub infinity/ = 7.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is derived at 298 K. An analysis of this result in terms of the statistical adiabatic channel model leads to a looseness parameter of a similarly ordered 0.94 A/sup -1/. The corresponding specific rate constants k(E,J) for dissociation of HO/sub 2/ are constructed and compared with trajectory calculations. The results are also compared with data on the reaction HO + O ..-->.. H + O/sub 2/ for which a nearly temperature-independent rate constant of 2.8 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ is predicted. An analysis of the limiting low-pressure rate coefficients with respect to energy-transfer properties is made. The results are compared with trajectory calculations of energy transfer of excited HO/sub 2/. 77 references, 8 figures, 5 tables.
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