UV Photodissociation Dynamics of Organic Hydroperoxides: Experiment and Theory.

The UV photodissociation dynamics of three organic hydroperoxides (ROOH, R = tert-butyl, cyclopentyl, and cyclohexyl) are examined experimentally at 282 nm utilizing velocity map imaging of the OH X²Π_3/2 (v″ = 0, J″) products. The three systems have similar O-O bond dissociation energies based on W1BD calculations and thus similar energy release to products. In each case, the experimental total kinetic energy release (TKER) distributions are bimodal, composed of narrow low and broad high TKER components extending over the available energy. The associated angular distributions of the OH X²Π products are isotropic, differing dramatically from those predicted for direct photodissociation. Complementary theoretical calculations map the relaxed potential energy profile for each ROOH along the steeply repulsive excited state (S₁) potential leading to RO + OH products. Low CCOO torsional barriers predicted along the ROOH dissociation pathway enable the OH products to recoil in many different directions, yielding isotropic angular distributions. Simple models of photodissociation suggest that the low TKER component arises from internal conversion to the ground state (S₀) potential, leading to a common RO + OH product asymptote. A simple impulsive model for dissociation captures some aspects of the high TKER component but neglects significant geometric changes in the alkyl substituent from ROOH to the RO product. This study provides new insight into the solar photolysis of organic hydroperoxides and the regeneration of OH radicals in atmospheric oxidation cycles.