Semi-empirical model fits femtosecond gas phase reaction kinetics

Two novel statistical kinetic models for the treatment of dispersive kinetics, based on a ‘Maxwell–Boltzmann distribution of molecular activation energies’, were recently reported for the treatment of homogeneous and heterogeneous solid-state processes, respectively, occurring over minutes or hours [P.J. Skrdla, R.T. Robertson, J. Phys. Chem. B 109 (2005) 10611]. Here, we show that the model equation originally developed to describe homogeneous (i.e., deceleratory) solid-state conversions can be applied with equal success to a gas phase reaction occurring on the femtosecond time-scale. This finding suggests that our simple, semi-empirical models may be sufficiently general to describe dispersive kinetics in a wide variety of chemical systems.