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@ARTICLE{Mitra:1024589,
author = {Mitra, Souvik and Heuer, Andreas and Diddens, Diddo},
title = {{E}lectron transfer reaction of {TEMPO}-based organic
radical batteries in different solvent environments:
comparing quantum and classical approaches},
journal = {Physical chemistry, chemical physics},
volume = {26},
number = {4},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2024-02263},
pages = {3020 - 3028},
year = {2024},
abstract = {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.},
cin = {IEK-12},
ddc = {540},
cid = {I:(DE-Juel1)IEK-12-20141217},
pnm = {1221 - Fundamentals and Materials (POF4-122) / DFG project
422726248 - SPP 2248: Polymer-basierte Batterien
(422726248)},
pid = {G:(DE-HGF)POF4-1221 / G:(GEPRIS)422726248},
typ = {PUB:(DE-HGF)16},
pubmed = {38179667},
UT = {WOS:001136882100001},
doi = {10.1039/D3CP04111E},
url = {https://juser.fz-juelich.de/record/1024589},
}