TY - JOUR
T1 - Reorganization Energy of Electron Transfer in Ionic Liquids
AU - Kodis, Gerdenis
AU - Ertem, Mehmed Z.
AU - Newton, Marshall D.
AU - Matyushov, Dmitry V.
N1 - Funding Information:
Research at ASU (D.V.M.) was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC0015641. The work at Brookhaven National Laboratory (M.Z.E) was carried out under contract DE-SC0012704 with the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, and utilized computational resources at both the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, and the Scientific Data and Computing Center, which is a component of the Computational Science Initiative, at Brookhaven National Laboratory under contract DE-SC0012704.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/4/14
Y1 - 2022/4/14
N2 - Bandshape analysis of charge-Transfer optical bands in room-Temperature ionic 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 result runs against common wisdom in the field since conducting ILs, which are 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 the 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.
AB - Bandshape analysis of charge-Transfer optical bands in room-Temperature ionic 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 result runs against common wisdom in the field since conducting ILs, which are 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 the 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.
UR - http://www.scopus.com/inward/record.url?scp=85128488497&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85128488497&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.2c00733
DO - 10.1021/acs.jpclett.2c00733
M3 - Article
C2 - 35389644
AN - SCOPUS:85128488497
SN - 1948-7185
VL - 13
SP - 3297
EP - 3303
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 14
ER -