ION-MOLECULAR CHARGE-TRANSFER REACTIONS OF HEXAFLUOROBENZENE AND CIS-DECALIN IN NONPOLAR SOLUTIONS STUDIED BY LINEWIDTH BROADENING IN MARY SPECTRA

The effect of an external magnetic field on the radiofluorescence aris ing from the recombination of spin-correlated radical ion pairs (MARY spectrum) has been studied for dilute nonpolar solutions of hexafluoro benzene and cis-decalin. MARY spectra of these systems show additional local fluorescence intensity maxima at zero field and in the field eq ual to triple the hfi constant. The breaking down of spin coherence in the course of the ion-molecular charge transfer reaction leads to bro adening of the maxima. Relations between the line broadening and the r ate of charge transfer reaction have been derived. Rate constants of c harge transfer reactions for hexafluorobenzene radical anion in squala ne and cis-decalin radical cation in hexane have been obtained experim entally.