Vibrational relaxation of highly excited diatomics. III. HF(v = 5, 6, 7)+H2, D2, N2, HF, CO2, N2O, CH4, and C2H6

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Abstract
Vibrational relaxation rate constants kQv are reported for HF (v = 5, 6, 7) collisions with eight quencher molecules Q = H2, D2, N2, HF, CO2, N2O, CH4, and C2H6, at 298 K under conditions of rotational equilibrium, using the fast flow infrared chemiluminescence technique. The rates are faster than had been reported by some investigators, the energy transfer probability PQv ranging from PH25 = 3.2×10−3 to PHF7 = 1.45. The rate constants rise with increasing v, i.e., n = 2.0 to 8.4 for different Q in the vn correlation. For all Q except H2 and HF, V-V transfer is suggested, but the Lambert–Salter plots have different slopes for different Q. The data are compared with published measurements and with theory, the latter especially for Q = HF.

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