Interfacial bond-breaking electron transfer in mixed water-ethylene glycol solutions: reorganization energy and interplay between different solvent modes.

ABSTRACT: We explore solvent dynamics effects in interfacial bond breaking electron transfer in terms of a multimode approach and make an attempt to interpret challenging recent experimental results (the nonmonotonous behavior of the rate constant of electroreduction of S2O8(2-) from mixed water-EG solutions when increasing the EG fraction; see Zagrebin, P.A. et al. J. Phys. Chem. B 2010, 114, 311). The exact expansion of the solvent correlation function (calculated using experimental dielectric spectra) in a series predicts the splitting of solvent coordinate in three independent modes characterized by different relaxation times. This makes it possible to construct a 5D free-energy surface along three solvent coordinates and one intramolecular degree of freedom describing first electron transfer at

SUBMITTER: Ismailova O 

PROVIDER: S-EPMC3725609 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature