Intermolecular Vibration-to-Vibration Energy Transfer in HF/DF(v=1) + HF/DF(v=1) yields HF/DF(v=0) + HF/DF(v=2) through the Formation of Dimers.

摘要

A theory of vibration-to-vibration energy transfer is developed for HF/DF(V=1) + HF/DF(V=1) yeilds HF/DF(V=0) + HF/DF(V=2) based on the model of dimer formation. This model is shown to be primarily responsible for the energy transfer below 500 K where a strong negative temperature dependence of energy transfer rates is found; above this temperature the rapid rotational motion of the colliding molecules cause the energy exchange to take place with the result that the rate increases with temperature in a normal fashion. The model represents the low-temperature limit of the energy-transfer process, while the rapid rotational model gives the high-temperatures limiting rate, so the overall collision process can be explained in terms of these two contributions.