Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

Abstract

A high-sensitive technique to detect O(1S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(1S) production process from the UV photodissociation of O3, N2O, and H2O2. The quantum yields for O(1S) formation from O3 photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10−4 and (5 ± 3) × 10−5, respectively. Based on thermochemical considerations, the O(1S) formation from O3 photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(1S)+O2(X3Σg −). Analysis of the Doppler profile of O(1S) produced from O3 photolysis at 193 nm also indicates that the O(1S) atoms are produced from the spin-forbidden process. In the photolysis of N2O and H2O2 at 193 nm, no discernible signal of O(1S) atoms has been detected. The upper limit values of the quantum yields for O(1S) production from N2O and H2O2 photolysis at 193 nm are estimated to be 8 × 10−5 and 3 × 10−5, respectively. Using the experimental results, the impact of the O(1S) formation from O3 photolysis on the atmospheric OH radical formation through the reaction of O(1S)+H2O has been estimated. The calculated results show that the contribution of the O(1S)+H2O reaction to the OH production rate is ∼2% of that of the O(1D)+H2O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(1S) at 557.7 nm have also been discussed.