TY  - JOUR
AU  - Mitra, Souvik
AU  - Heuer, Andreas
AU  - Diddens, Diddo
TI  - Electron transfer reaction of TEMPO-based organic radical batteries in different solvent environments: comparing quantum and classical approaches
JO  - Physical chemistry, chemical physics
VL  - 26
IS  - 4
SN  - 1463-9076
CY  - Cambridge
PB  - RSC Publ.
M1  - FZJ-2024-02263
SP  - 3020 - 3028
PY  - 2024
AB  - In this study, we delve into the complex electron transfer reactions associated with the redox-active (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), a common component in organic radical batteries (ORBs). Our approach estimates quantum electron-transfer (ET) energies using Density Functional Theory (DFT) calculations by sampling from structures simulated classically. This work presents a comparative study of reorganization energies in ET reactions across different solvents. Furthermore, we investigate how changes in the electrolyte environment can modify the reorganization energy and, consequently, impact ET dynamics. We also explore the relationship between classical and quantum vertical energies using linear regression models. Importantly, this comparison between quantum and classical vertical energies underscores the role of quantum effects, like charge delocalization, in offering added stabilization post-redox reactions. These effects are not adequately represented by the classical vertical energy distribution. Our study shows that, although we find a significant correlation between the vertical energies computed by DFT and the classical force field, the regression parameters depend on the solvent, highlighting that classical methods should be benchmarked by DFT before applying them to novel electrolyte materials.
LB  - PUB:(DE-HGF)16
C6  - 38179667
UR  - <Go to ISI:>//WOS:001136882100001
DO  - DOI:10.1039/D3CP04111E
UR  - https://juser.fz-juelich.de/record/1024589
ER  -