The pulsed-dye laser-induced photooxidation of ZnTPP by benzoquinone has been studied with time-resolved direct-detected electron spin resonance (ESR). Spectra of free radicals can be obtained within 1 µ$ after the laser pulse. For the first time the ESR spectra of both the anion and cation radicals generated in the electron-transfer reaction have been observed. The time-resolved spectra show triplet and radical pair spin polarization (CIDEP) effects that can be linked to the mechanism of the photoinduced charge separation reaction. The CIDEP effects give semiquantitative data on rate constants.
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