An investigation of the processes controlling ozone in the upper stratosphere

Photolysis of vibrationally excited oxygen produced by ultraviolet photolysis of ozone in the upper stratosphere is incorporated into the Lawrence Livermore National Laboratory 2-D zonally averaged chemical-radiative-transport model of the troposphere and stratosphere. The importance of this potential contributor of odd oxygen to the concentration of ozone is evaluated based upon recent information on vibrational distributions of excited oxygen and upon preliminary studies of energy transfer from the excited oxygen. When the energy transfer rate constants of previous work are assumed, increases in model ozone concentrations of up to 40 percent in the upper stratosphere are found, and the ozone concentrations of the model agree with measurements, including data from the Upper Atmosphere Research Satellite. However, the increase is about 0.4 percent when the larger energy transfer rate constants suggested by more recent experimental work are applied in the model. This indicates the importance of obtaining detailed information on vibrationally excited oxygen properties to evaluation of this process for stratospheric modelling.