| Abstract: | It is shown that the master equation describing fall-off effects in unimolecular and recombination reactions, with angular momentum (J) conservation taken into account, can be solved exactly if the assumption is made that the probability of collisional energy transfer in J is independent of initial state; this assumption is shown to be physically acceptable (from general conservation considerations and from trajectory calculations) for typical neutral radical recombination and decomposition reactions. This leads to a J-averaged master equation which can be readily solved by standard means. Illustrative computations using this treatment are presented. |
