Laser double resonance measurements of vibrational energy transfer rates and mechanisms in HF(v = 2)

Abstract

Overtone vibration‐laser double resonance studies of HF(v = 2) yield self‐relaxation rate constants for v = 2 and v = 1 of k₂ = (19.8±1.0) ×10⁻¹² cm³ molecule⁻¹ s⁻¹ and k₁ = (1.46±0.1) ×10⁻¹² cm³ molecule⁻¹s⁻¹, respectively. These experiments indicate that the fraction of HF(v = 2) molecules relaxing via vibration‐to‐vibration energy transfer is only 0.35±0.10, in sharp contrast to trajectory and scaling calculations which predict the dominance of this pathway over vibration‐to‐translation, rotation energy transfer.