title: Radical Cage Effects: Comparison of Solvent Bulk Viscosity and Microviscosity in Predicting the Recombination Efficiencies of Radical Cage Pairs.
abstract: This study reports the results of experiments that probed how solvents affect the recombination efficiency (FcP) of geminate radical cage pairs. The macroviscosity of solvents has traditionally been used to make quantitative predictions about FcP, but experiments reported here show that FcP varies dramatically for solvent systems with identical macroviscosities. Experiments show that FcP correlates with the solvent microviscosity: five different solvent systems (consisting of a solvent and a structurally similar viscogen) were examined, and FcP was the same for all five solvent systems at any particular microviscosity. The translational diffusion coefficient of the radicals (measured by DOSY) in the solvent system was used to define the microviscosity of the solvent system.
authors.affiliation: Department of Chemistry and Biochemistry, University of Oregon , 1253 University of Oregon, Eugene, Oregon 97403, United States.
authors.forename: Justin T
authors.initials: JT
authors.lastname: Barry
authors.affiliation: Department of Chemistry and Biochemistry, University of Oregon , 1253 University of Oregon, Eugene, Oregon 97403, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Berg
authors.affiliation: Department of Chemistry and Biochemistry, University of Oregon , 1253 University of Oregon, Eugene, Oregon 97403, United States.
authors.forename: David R
authors.initials: DR
authors.lastname: Tyler