Vibration–vibration energy transfer in laser excited SO2: Further evidence for a slow V–V step

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Abstract
The rate of fluorescence rise and fall has been measured for the ν3 state of SO2 as a function of pressure in pure SO2 and SO2−rare gas mixtures pumped by a Q−switched CO2 laser. The results of these experiments are consistent with rapid equilibration of ν1 and ν3 stretching modes (∼135 collisions) followed by a very slow equilibration of the ν1, ν3 stretches with the ν2 bend (∼2600 collisions) in pure SO2. The presence of metastable, vibrationally hot stretching modes with vibrationally cold bending modes suggests the possibility of achieving a population inversion in SO2 by infrared laser pumping. The parameters and possibilities for obtaining vibrationally selective chemical reactions in SO2 are considered.

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