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The rate constants of the three-body recombination reaction + 02 + (M = He, N2, H20) were measured from 4.79 to 30.1 Torr at room temperature by the discharge-flow technique. The respective rate constants obtained are (2.6 ± 0.2) X 10~32, (6.1 ± 0.9) X 10-32, and (6.4 ± 0.8) X 10'31 cm6 s"1. Although the rates for He and N2 can be rationalized in terms of existing theory, that for H20 implies a collision efficiency greater than 1. This situation can be rectified by use of the total quantum mechanical scattering cross section instead of the Lennard-Jones cross section commonly used.

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We have studied the unimolecular reaction C 6 H 5 CI+-+C6H5+ + CI as a function of internal energy by using multi photon ionization (MPI) on a supersonically cooled jet of chlorobenzene to prepare the excited parent ion. Specific rate constants k (E) were obtained from an analysis of the distorted C6HS+ peak shape in a time-of-flight (TOF) mass spectrometer. Decomposition in the wavelength region 265-270 nm is shown to proceed by two-photon ionization followed by onephoton absorption. The internal energy of the excited parent ion is characterized in a separate experiment which measures the photoelectron kinetic energy distribution, obtained over the same wavelength range. The specific rate constants found in this study compare well with previous literature values, thus validating this MPI TOF technique for the determination of ion decomposition rates.

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