Photoinduced electron transfer to triplet flavins. Correlation between the volume change-normalized entropic term and the Marcus reorganization energy.

The data obtained through the application of nanosecond laser-induced optoacoustic spectroscopy (LIOAS) to several electron donor-acceptor pairs in aqueous solution were analyzed together with the respective experimentally determined Marcus reorganization energy. Acceptors were the flavin mononucleotide and flavin-adenine dinucleotide triplet states (3FMN and 3FAD) and donors were tryptophan, tyrosine, histidine, triethanolamine, and ethylenediaminetetraacetic acid. The respective calculated Gibbs energy for electron transfer, Delta(ET)G degrees , was used together with the enthalpy change for the formation of free radicals, Delta(FR)H, obtained from the LIOAS data, to derive the entropy change for the formation of the radicals, Delta(FR)S. In all cases, variation of the monovalent cations, i.e., [CH3(CH2)3]4N+, Li+, NH4+, K+, and Cs+, resulted in variation of the enthalpy change, Delta(FR)H, and in the structural volume change, Delta(FR)V, for the free-radical production, both derived from LIOAS. Delta(FR)H and Delta(FR)V linearly correlated with each other within the cation series. From this correlation the respective entropic term TDelta(FR)S was derived as well as the ratio X = TDelta(FR)S/Delta(FR)V for each of the pairs. X linearly correlated with the respective total Marcus reorganization energy, lambda, for all systems analyzed. This observation underlines the concept that both lambda and Delta(FR)V respond to the same phenomena. The correlation also offers an experimental approach for the understanding at a molecular level of the origin of the lambda values as well as for their evaluation.