Collisional energy transfer via vibrational predissociation: Relaxation of HF(v=1) by HF dimers

Overtone vibration–laser double resonance measurements determine the vibrational relaxation rate of HF(v=1) by HF dimers. Vibration-to-vibration energy transfer from the excited monomer to the dimer followed by vibrational predissociation of the dimer provides an efficient pathway for vibration-to-translation energy transfer that deexcites the monomer at 40% of the gas kinetic collision rate. Analysis of the pressure dependence of the observed decay constants using a simple kinetic model establishes a rough upper limit of 10 ns on the predissociation lifetime of the collisionally excited dimer.