The measurement of rapid rate processes by kinetic spectroscopy during a photolysis flash; vibrational relaxation of NO X 2 II from levels v 2

Abstract

The recording of transient changes in optical density that take place during the period of a photolysis flash can, in principle, allow measurement of the kinetics of photo-processes having half-lives an order of magnitude less than the rise or decay time of the flash itself. The construction and use of a sensitive, ‘split-beam’ kinetic spectrophotometer is described, which permits the detection of transient changes in optical density > 0.01 and the measurement of half-lives >1 (us. The apparatus has been used to study the relaxation of NOX 2 II from its first and second excited vibrational levels in the presence of N 2 0 or CH4 and/or Ar. The efficiency of vibrational energy exchange with N 2 0 decreases with the vibrational quantum number of the excited level and this is shown to be consistent with the reduction in the vibrational spacing caused by anharmonicity. The measured collision numbers are in good agreement with those calculated on the baste of an empirical correlation (Callear 1965).