Temperature effects in the collisional deactivation of highly vibrationally excited pyrazine by unexcited pyrazine

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Abstract
Time-dependent infrared fluorescence (IRF) from the C–H fundamental and overtone bands was used to monitor the vibrational deactivation (by unexcited pyrazine) of pyrazine excited at 308 nm with a pulsed laser. The 1-color and 2-color IRF results were modeled with collisional master equation calculations in order to determine the temperature dependence of the energy transfer parameters. The experimental data cannot be modeled without invoking a biexponential collision step size distribution, which implies that ‘‘super collisions’’ are significant. The results show that the energy transfer parameters are essentially constant at temperatures greater than the Lennard–Jones well depth, but at lower temperatures, energy transfer is enhanced. It is likely that vibration–vibration energy transfer dominates in this system.