Temperature-dependent kinetics study of the reactions of O(1D2) with N2 and O2

A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics of the reactions of electronically excited oxygen atoms, O(1D2), with N2 (k1) and O2 (k2) as a function of temperature (197–427 K) in helium buffer gas at pressures of 11–40 Torr. The results are well-described by the following Arrhenius expressions (units are 10-11 cm3 molecule-1 s-1): k1(T ) ¼ (1.99 Æ 0.06) exp{(145 Æ 9)/T} and k2(T ) ¼ (3.39 Æ 0.03) exp{(63 Æ 3)/T}. Uncertainties in the Arrhenius parameters are 2s and represent precision only; estimated accuracies of reported k1(T ) and k2(T ) values at the 95% confidence level are Æ10% around room temperature and Æ15% at the temperature extremes of the study. The O(1D2) þ O2 kinetic data reported in this study are in very good agreement with available literature values. However, the kinetic data reported in this study (and two other new studies reported in this issue) suggest that the O(1D2) þ N2 reaction is significantly faster than previously thought, a finding that has important implications regarding production rates of tropospheric HOx radicals as well as stratospheric HOx and NOx radicals calculated in atmospheric models.