P. Chaquin et al., EXPERIMENTAL AND THEORETICAL-STUDY OF THE XYO (X, Y = CL, BR) LIGHT-INDUCED INTERCONVERSION IN ARGON MATRIX, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 102(43), 1998, pp. 8222-8229
The complex ClBrO has been generated in argon matrix by photolysis of
the O-3:BrCl complex and has been characterized by its Fourier-transfo
rm IR spectrum. Wavelength dependence of ClBrO photochemistry has been
determined in the range from 317 to 870 nm by using laser irradiation
s and in the frequency region of a Nernst globar. Visible irradiation
between 633 and 700 nm transforms ClBrO into BrClO and that above 700
nm continues the transformation into BrOCl. Reverse photoisomerization
of BrOCl into ClBrO or BrClO was not observed. BrClO but not ClBrO is
sensitive to IR irradiation. Calculations are combined with experimen
tal observations to present a model for the photochemical isomerizatio
n of ClBrO and a comparison with related Cl2O and Br2O isomerizations.