Reorganization Energy of Electron Transfer in Ionic Liquids

Bandshape analysis of charge-transfer optical bands in room-temperatureionic liquids (ILs) was performed to extract the reorganization energy of electron transfer.Remarkably, the reorganization energies in ILs are close to those in cyclohexane. This resultruns against common wisdom in thefield since conducting ILs, which are characterized byan infinite static dielectric constant, and nonpolar cyclohexane fall to the opposite ends ofthe polarity scale based on their dielectric constants. Theoretical calculations employingstructure factors of ILs from molecular dynamics simulations support the low values of thereorganization energy. Standard dielectric arguments do not apply to solvation in ILs, andnonergodic reorganization energies are required for a quantitative analysis.

Automated summary

This article investigates the reorganization energy of electron transfer in room-temperature ionic liquids (ILs) and finds that it is similar to that in cyclohexane. This result contradicts common knowledge, as ILs and cyclohexane have different polarities. The study also utilizes molecular dynamics simulations to support the conclusion of low reorganization energy.