Reorganization Energy of Electron Transfer in Ionic Liquids

Kodis, Gerdenis; Ertem, Mehmed Z.; Newton, Marshall D.; Matyushov, Dmitry V.

doi:10.1021/acs.jpclett.2c00733

Reorganization Energy of Electron Transfer in Ionic Liquids

Journal Article · Thu Apr 07 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00733· OSTI ID:1871818

Kodis, Gerdenis ^[1]; ^[2]; ^[2]; ^[1]

Arizona State Univ., Tempe, AZ (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

We report bandshape analysis of charge-transfer optical bands in room-temperature ionic liquids (ILs) is performed to extract reorganization energy of electron transfer. Remarkably, the reorganization energies in ILs are close to those in cyclohexane. This result runs against common wisdom in the field since conducting ILs, characterized by an infinite static dielectric constant, and nonpolar cyclohexane fall to the opposite ends of the polarity scale based on their dielectric constants. Theoretical calculations employing structure factors of ILs from molecular dynamics simulations support low values of the reorganization energy. Standard dielectric arguments do not apply to solvation in ILs and nonergodic reorganization energies are required for a quantitative analysis.

View Accepted Manuscript (DOE)

Research Organization:: Arizona State University, Tempe, AZ (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0015641

OSTI ID:: 1871818

Alternate ID(s):: OSTI ID: 2367324

Report Number(s):: BNL--223061-2022-JAAM

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 14 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Reorganization Energy of Electron Transfer in Ionic Liquids

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