Department of Physics and School of Molecular Sciences, Arizona State University, PO Box 871504, Tempe, Arizona 85287-1504, United States.
Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973-5000, United States.
J Phys Chem Lett. 2022 Apr 14;13(14):3297-3303. doi: 10.1021/acs.jpclett.2c00733. Epub 2022 Apr 7.
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.
对室温离子液体 (ILs) 中的电荷转移光带进行了带形分析，以提取电子转移的重组能。值得注意的是，ILs 中的重组能与环己烷中的重组能接近。这一结果与该领域的常识相悖，因为具有无限静态介电常数的导电 ILs 和非极性环己烷根据介电常数落在极性尺度的相反两端。采用分子动力学模拟的 ILs 结构因子的理论计算支持低重组能值。标准介电论点不适用于 ILs 中的溶剂化，需要非遍历重组能进行定量分析。
