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The direct photolysis of 25 individual polychlorinated diphenyl sulfides (PCDPSs) substituted with 1-7 chlorine atoms was investigated using a 500-W Xe lamp. Photolysis of PCDPSs followed pseudo-first-order kinetics, with the higher chlorinated diphenyl sulfides generally degrading faster than the lower chlorinated congeners. A quantitative structure-activity relationship model to predict the photolysis rates of PCDPSs was developed using 16 fundamental quantum chemical descriptors. We found that the substitution pattern for chlorine atom