Modeling Collisional Transitions in Thermal Unimolecular Reactions: Successive Trajectories and Two-Dimensional Master Equation for Trifluoromethane Decomposition in an Argon Bath.

Collisional transition processes in thermal unimolecular reactions are modeled by collision frequency, Z, and probability distribution function, P(E, J; E', J'), which describes the probabilities of collisional transitions from the initial state specified by the total energy and angular momentum, (E', J'), to the final states, (E, J). The validity of the collisional transition model, consisting of Z and P(E, J; E', J'), is assessed here for the title reaction. The present model and its parameters are derived from the moments of transition probabilities calculated by classical trajectory simulations. The model explicitly accounts for coupling between the energy and angular momentum transfer and the dependence of transition probability on the initial state. The performance of the model is evaluated by comparing the rate constants calculated by solving the two-dimensional master equation with those obtained from the classical trajectory calculations of the sequence of successive collisions. The rate constants are also compared with available experimental data. The present collisional transition model is found to perform fairly well for predicting the pressure-dependent rate constants. The uncertainty in the prediction and sensitivities of the rate constants to the model parameters are discussed. A simplified version of the model is proposed, which performs as well as the full model. The simplifications and robust procedures for calculating the model parameters are described.