Photodissociation dynamics of cumene hydroperoxide at 248 and 193 nm

초록

Photodissociation dynamics of cumene hydroperoxide at 248 and 193 nm producing (C<inf>6</inf>H<inf>5</inf>)(CH<inf>3</inf>)<inf>2</inf>CO (CumO) and OH fragments has been investigated by measuring laser induced fluorescence spectra of the OH fragments, which are produced exclusively in the ground electronic state. The measured energy distributions among the fragments are f<inf>r</inf>(OH) = 0.03, f<inf>t</inf> = 0.49, f<inf>int</inf>(CumO) = 0.48 and f<inf>r</inf>(OH) = 0.03, f<inf>t</inf> = 0.18, f<inf>int</inf>(CumO) = 0.79 at 248 and 193 nm, respectively, and negligible vibrational excitation in OH was observed at both wavelengths. At 248 nm, slightly negative μ-ν and positive ν-J vector correlations were observed by analyzing the Doppler profiles of the rotationally resolved OH spectra, whereas no vector correlations were observed at 193 nm. From the measurements, detailed photodissociation dynamics of cumene hydroperoxide is discussed compared to the case of tert-butyl hydroperoxide previously studied.