Test of the procedure for obtaining detailed endothermic rate constants from microscopic reversibility

Abstract

Experimental data concerning the effect of varying reagent vibrational, rotational and translational energy on the rates of endothermic reactions can be obtained from the application of microscopic reversibility to the corresponding exothermic processes. A 3D classical trajectory computation has been performed to test this procedure. On the basis of this study we conclude that the ‘triangle plots’ of endothermic detailed rate constants published previously can be depended on to 5–10% theoretical accuracy (expressed as a percentage of the maximum endothermic rate constant).