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Significance The photolysis of hydrogen peroxide produces OH radicals and has enormous environmental and technological relevance. Experiments have shown that the absorption cross-sections beyond 290 nm (solar radiation reaching the Earth’s surface) are not very different in the gas phase and in bulk water solution, and hence comparable photolytic rate constants are found in these two media. Computer simulations reported in the present article reveal, however, that the situation changes dramatically when hydrogen peroxide is adsorbed on surfaces. The results emphasize the role of the local electric field and describe a nonlinear variation of the absorption cross-sections with field strength. The implications of this finding are discussed.

Tight electrostatic regulation of the OH production rate from the photolysis of hydrogen peroxide adsorbed on surfaces