Production of OH from photolysis of HOCl at 307-309 nm

Laser-induced fluorescence has been used to measure the amount of OH produced in the laser photolysis of HOCl at 310 nm. The HOCl was generated by the Cl2O + H2O and by the HCl + Cl2O reactions. The laser technique samples OH on a microsecond time scale so that secondary radical reactions cannot contribute significantly to the observed signals. The fluorescence signals were calibrated with O3-H2O mixtures, the reactions O3 + h(nu) yields O(1D) + O2 and O(1D) + H2O yields 2OH yielding known amounts of OH. The value for the absorption cross section of HOCl at 310 nm has been determined to be 6 x 10 to the -20th sq cm, assuming K(eq) = 0.082 for the Cl2O + H2O yields 2HOCl system and assuming unit quantum yield for the production of OH. The present investigation further supports earlier experimental work concluding that HOCl will photodissociate rapidly and will not be an important holding tank for chlorine in the stratosphere. These results are in disagreement with theoretical calculations of the UV absorption spectrum of HOCl in the 300-350-nm wavelength region.