In Stationary Regime, Electron Transfer Rates in RTIL Media Are Diffusion Controlled: Experimental Evidence from Pulse Radiolysis Study

Abstract

We report electron transfer (ET) process from the long-lived radical anions of pyrene and benzophenone to molecular acceptors, e.g., benzophenone and fluorenone, respectively, in two RTIL media, namely, [BMIM][PF6] and [BMIM][BF4], as well as a few other conventional organic solvents using the nanosecond pulse radiolysis technique. Decay of the donor radical anion and concomitant formation of the acceptor radical anion ensure a bimolecular ET process. The rate constants for the bimolecular ET process in both normal organic solvents and RTILs have been found to be nearly equal to diffusion controlled rate calculated for the corresponding solvent. For long-lived anions, having lifetimes longer than a few hundred nanoseconds, quenching occurs mainly in the stationary regime. In this regime, the ET rate is fully controlled by the rate of diffusion of the reactive species in those solvents. To the best of our knowledge, this is the first experimental evidence of the diffusion controlled ET process occurring in the stationary regime in RTIL media.