A theoretical analysis of photoactivated unimolecular dissociation: The overtone dissociation of t-butyl hydroperoxide

We have used the master equation formalism to analyze the photoactivated unimolecular dissociation of a large polyatomic molecule, t-butyl hydroperoxide (t-BuOOH). Our results are compared to the experimental results of Chandler, Farneth, and Zare and of Chuang et al. We find that the curvature in their Stern-Volmer plots cannot be explained by a collisional energy transfer mechanism. At high pressure, the theoretical Stern–Volmer plots are linear, independent of the collisional energy transfer properties. This linearity is related to the existence of a limiting high pressure ‘‘reactive distribution.’’ We identify three different pressure regimes that exist in photoactivated unimolecular reaction experiments, and we relate these regimes to the properties of the reactive distribution. In particular, we find that, when a Stern-Volmer analysis is used, curvature at very low pressure can result in systematic errors in determining the unimolecular rate constants. In addition, we have successfully analyzed the real time experiments of Rizzo and Crim using the same molecular model and parameters necessary to predict the experiments of Chandler et al.