A direct determination of the role of vibration-to-vibration energy transfer in HF(v=3,4) self-relaxation

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Abstract
Overtone vibration‐laser double resonance directly measures the relative importance of vibration‐to‐vibration and vibration‐to‐translation‐and‐rotation energy transfer for HF(v=3 and v=4) at room temperature. The fraction of HF(v) molecules relaxing by V–V energy transfer is 0.44±0.05 and 0.16±0.05 for v=3 and v=4, respectively, compared to 0.59±0.10 for v=2. These measurements show that V–T,R energy transfer is the dominant relaxation mechanism for HF(v≥3) and the observed decreased amount of V–V energy transfer for higher initially excited vibrational levels is in good agreement with a chemiluminescence measurement and several theoretical calculations. The data demonstrate that the magnitude of the energy defects for the component pathways primarily determines the energy transfer mechanism for HF(v=2–4).