Journal Article

FZJ-2024-02263

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Electron transfer reaction of TEMPO-based organic radical batteries in different solvent environments: comparing quantum and classical approaches

Mitra, S.Extern* ; Heuer, A.FZJ* ; Diddens, D. (Corresponding author)FZJ*

2024
RSC Publ. Cambridge

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Please use a persistent id in citations: doi:10.1039/D3CP04111E  doi:10.34734/FZJ-2024-02263

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.

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Contributing Institute(s):

1. Helmholtz-Institut Münster Ionenleiter für Energiespeicher (IEK-12)

Research Program(s):

1. 1221 - Fundamentals and Materials (POF4-122) (POF4-122)
2. DFG project 422726248 - SPP 2248: Polymer-basierte Batterien (422726248) (422726248)

Appears in the scientific report 2024

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF < 5 ; JCR ; National-Konsortium ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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