Energy-dependent collisional deactivation of vibrationally excited azulene

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Abstract
Collisional energy transfer parameters for highly vibrationally excited azulene have been deduced from new infrared fluorescence (IRF) emission lifetime data with an improved calibration relating IRF intensity to vibrational energy [J. Shi, D. Bernfeld, and J. R. Barker, J. Chem. Phys. 88, 6211 (1988), preceding paper]. In addition, data from previous experiments [M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983)] have been reanalyzed based on the improved calibration. Inversion of the IRF decay curves produced plots of energy decay, which were analyzed to determine 〈ΔE〉, the average energy transferred per collision. Master equation simulations reproduced both the original IRF decays and the deduced energy decays. A third (simple) method of 〈ΔE〉 determination agrees well with the other two. The results show 〈ΔE〉 to be nearly directly proportional to the vibrational energy of the excited azulene from ∼8000 to 33 000 cm−1. At high energies, there are indications that the 〈ΔE〉 energy dependence may be slightly reduced.