Abstract
The first-order rate constants for the decomposition of Na[ClO3] and Na[ClO4] when studied by X-p.e.s. are shown to have a linear dependence on the intensity of the ionising radiation used. A simple steady-state model, which emphasises the rôle of molecular excitons in the decomposition process, is constructed to explain this behaviour. Variable temperature studies in the range 293–113 K indicate that the rate of photo-induced decomposition of Na[ClO3] increases as the temperature is lowered, and analysis of the mode of decomposition suggests that the temperature-dependence arises from thermal deactivation of the molecular exciton, [ClO* 3].

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