Trends in organic hydroperoxide photodissociation and absorption cross sections between 266 and 377 nm

Abstract

Organic hydroperoxides have atmospheric roles in secondary organic aerosol formation and maintaining OH radical concentrations. Monitoring OH from CH3CH2OOH and (CH3)3COOH at 266, 291, 331, 362, and 377nm yields trends in energy disposal and absorption cross sections. Nascent OH radicals emerge similarly, but with less translational energy from the heavier parent. Cross sections are new for CH3CH2OOH and extend the range for (CH3)3COOH, which has implications for modeling atmospheric OH concentrations. Lower cross sections and higher OH rotation for (CH3)3COOH <331nm could be due to a higher trans barrier for torsion about the O–O bond, compared to CH3OOH and CH3CH2OOH.