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Abstract
A study of the temperature dependence (from 233 to 353 K) of the rate of back electron-transfer reactions within geminate radical pairs by measurement of the free radical yield is reported. The radical pair is generated by photoinduced electron transfer with rhodamine 6G and oxazine 118 cations as electron acceptors and aromatic amines and methoxy-benzene derivatives as electron donors in acetonitrile, methanol and ethanol. In acetonitrile, the back electron transfer is non-adiabatic and apparent negative activation energies are observed for barrierless reactions. In alcohol solvents, an anomalously large temperature dependence is observed, which is attributed to a solvent-controlled adiabatic behaviour.
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