Photodissociation Dynamics of t-butyl Hydroperoxide at 280-285 nm

초록

The phodissociation dynamics of t-butyl hydroperoxide at 280-285 nm has been investigated by measuring laser induced fluorescence spectra of the fragment OH. Measured fractions of the available energy distributed among the fragments are f<inf>t</inf>=0.56, f<inf>r</inf>(OH)=0.044, f<inf>int</inf>(t-BuO)=0.40, and negligible populations of OH are found in vibrationally excited states. By analyzing the Doppler profiles of the spectra of OH, the positive v-J vector correlation has been obtained. From the measured v-J correlation and A' propensity in the two A-doublets of OH, it is concluded that the dissociation takes place directly from the repulsive surface induced by the σ* ← n transition with the fragment OH rotating in the plane perpendicular to the dissociating O-O bond axis.