VIBRATIONAL-RELAXATION OF OH(X2-PI-I, V=1-3) BY O-2

Rate constants for OH(X2Πi, v = 1-3) vibrational relaxation induced by nonreactive collision with O2 have been measured. OH(v) is created by the H + O3→OH(v≤9) + O 2 reaction in an electron-irradiated O3, H2, Ar mixture. OH(v) fundamental and first overtone IR emission is observed using time-resolved Fourier spectroscopy. Spectral fitting followed by kinetic fitting of the resultant populations using a single-quantum relaxation model yields rate constants of kv=1 = (1.3 ± 0.4)×10-13, kv=2 = (2.1 ± 0.3)×10-13, kv=3 = (2.9±0.8) ×10-13 (all units are in cm3/s). Our measurements are consistent with and extend published results on the same system, as well as predictions made by Schwartz-Slawsky-Herzfeld theory. © 1990 American Institute of Physics.