ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Overtone vibration–laser double resonance studies of DF(v=1–3) energy transfer yield self-relaxation rate constants for v=1, 2 and 3 of k1=(0.37±0.06)×10−12 cm3 mol−1 s−1, k2=(22.0±2.0)×10−12 cm3 mol−1 s−1, and k3=(17.0±1.8)×10−12 cm3 mol−1 s−1, respectively. The approach also directly measures the relative importance of vibration-to-vibration (V–V) and vibration-to-translation-and-rotation (V–T,R) energy transfer. The fraction of DF(v) molecules relaxing by V–V energy transfer is 1.1±0.1 and 0.72±0.10 for v=2 and v=3, respectively. Essentially all of the vibrational energy transfer in v=2 occurs via the V–V mechanism. The slower relaxation of DF(v=3) compared to DF(v=2), in contrast to simple scaling law predictions, reflects the decreasing influence of the V–V mechanism, even though it is still the primary relaxation pathway for DF(v=3). Comparison with HF self-relaxation qualitatively indicates that V–R energy transfer is important in V–T,R relaxation of DF(v=1).
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.458853
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