Vibrational relaxation of HF(v = 3,4,5)

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Abstract
Measurements of laser excited vibrational overtone fluorescence show that the self-relaxation rates for HF(v = 3,4,5) are (3.02±0.30)×10−11, (7.28±0.27)×10−11, and (15.1±0.8)×10−11 cm3 molecule−1 s−1, respectively, and that single vibrational quantum energy transfer is the dominant relaxation path. The relaxation rates scale as v2.7 and are independent of initial rotational quantum number up to J = 3. The large energy transfer probabilities are consistent with the significant contribution from orbiting collisions found in trajectory calculations, and comparing the measurements to several calculations demonstrates the importance of including vibration–rotation coupling in the theory.