Microcanonical Rate Constants for Unimolecular Reactions in the Low-Pressure Limit

Low-pressure-limit microcanonical rate constants, κ0(E,J), describe the rate of activating bath gas collisions in a unimolecular reaction and are calculated here using classical trajectories and quantized thresholds for reaction. The resulting semiclassical rate constants are two-dimensional (in total energy E and total angular momentum J) and are intermediate in complexity between the four-dimensional state-to-state collisional energy and angular momentum transfer rate constant, R(E′,J′;E,J), and the highly averaged thermal rate constant, k0. Results are presented for CH4 (+M), C2Hx (+M), x = 3–6, and H2O (+M), where κ0(E,J) is shown generally to be a sensitive function of the bath gas, temperature, and initial state of the unimolecular reactant. Strong variations in κ0 with respect to E and J lead to complex trends in relative microcanonical bath gas efficiencies. This underlying complexity may complicate the search for simple explanations for observed trends in relative thermal bath gas efficiencies. A different measure of the microcanonical collision efficiency that describes the energy range of activating collisions is introduced that supports the empirical decomposition of collisional activation into separable translational-to-vibrational and rotational-to-vibrational activation mechanisms. The two mechanisms depend differently on mass, temperature, and the J-dependence of the threshold energy for reaction, with rotational-to-vibrational activation favored for heavier baths and for reactions with rigid transition states. Finally, κ0 is used to test the accuracy of several two-dimensional models for R that were proposed for use in master equation studies.