The formation of excited states of N,N,N',N'-tetramethyl-p-phenylenediamine in irradiated nonpolar liquids

The yield of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) excited states, G/sub s/, has been obtained in irradiated tetramethylsilane, isooctane, cyclopentane, n-hexane, and cyclohexane as a function of TMPD concentration, c, over the range c = 0.5 x 10/sup -3/-50 x 10/sup -3/ M. In tetramethylsilane and isooctane, G/sub s/ is found to be linear on c as would be expected on the basis of a nondiffusional transfer of the solvent ion positive charge to TMPD followed by recombination of TMPD/sup +/ with the geminate electron. In cyclopentane, n-hexane, and cyclohexane, G/sub s/ becomes increasingly concave downward in its depedence on c. This concavity is attributed to an increasing contribution to G/sub s/ from excited states of the solvent that nonradiatively transfer their energy to TMPD. Optical excitation of cyclohexane at 147 nm and measurement of the quenching of its fluorescence by TMPD confirm this view.