Determination of Relative Triplet Sublevel Populating Rates During Optical Pumping Using ODMR

A method is introduced, based on optical detection of triplet state magnetic resonance (ODMR), to determine the relative populating rates of photoexcited triplet state sublevels during optical pumping. Phosphorescence transients induced by microwave rapid passage during optical pumping are analyzed globally utilizing kinetic parameters obtained from separate microwave-induced delayed phosphorescence measurements to obtain relative sublevel populating rates. Results are unaffected by phosphorescence from triplet populations that do not yield an ODMR response. The method is applied to the triplet state of the indole chromophore in various environments to reveal the effects of local interactions on the pattern of intersystem crossing. Enhanced spin--orbit coupling effects are attributed to interactions that reduce the planar symmetry of the indole chromophore.