Vibrational relaxation of OH(X 2Πi, v=1–3) by O2

Abstract

Rate constants for OH(X ²Π_i, 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)+O₂ 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 k_v=1 =(1.3±0.4)×10⁻¹³, k_v=2=(2.1±0.3)×10⁻¹³, k_v=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.