PHOTODISSOCIATION DYNAMICS OF T-BUTYL-HYDROPEROXIDE AT 280-285 NM

The phodissociation dynamics of t-butyl hydroperoxide at 280-285 MI ha s been investigated by measuring las-er induced fluorescence spectra o f the fragment OH. Measured fractions of the available energy distribu ted among the fragments are f(r)=0.56, f(r)(OH)=0.044, f(int)(t-BuO)=0 .40, and negligible populations of OH are found in vibrationally excit ed states. By analyzing the Doppler profiles of the spectra of OH, the positive nu-J vector correlation has been obtained. From the measured nu-J correlation and A '' propensity in the two Lambda-doublets of OH , it is concluded that the dissociation takes place directly from the repulsive surface induced by the sigma<--n transition with the fragme nt OH rotating in the plane perpendicular to the dissociating O-O bond axis.