The Liouville space algebraic expression for the current-induced fluorescence can be written down readily 1 from the double-sided diagram shown in Fig. (1a). We get, S (1) (ω s) = 1 h 4 Re iα |T iα | 2 t −∞ dτ e −iωs(t−τ) τ −∞ dτ 1 τ −∞ dτ 2 e ī h α(τ2−τ1) f α (α) Tμ † sR (t)μ sL (τ)ĉ † iL (τ 1)ĉ iR (τ 2) (1

This research elucidates the intricate nature of electronic coupling values for the redox-active (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) often used in organic radical batteries (ORBs), employing a combination of classical molecular dynamics (MD) and multiconfigurational simulations, i.e., the Complete active space self-consistent field (CASSCF) methods. Our study reveals the significant influence of both distance and relative orientation of the redox pairs (TEMPO and TEMPO+) on the electronic coupling. Thus, our simulations suggest that the electronic communication between the redox centres and this the charge mobility heavily depends on both - TEMPO's intrinsic molecular properties as well as the supramolecular environment in the electrode material. Additionally, our study highlights the limitations of the frontier molecular orbital (FMO) method in this context. Our findings underscore the significance of integrating molecular dynamics and advanced electronic structure methods, like CASSCF, to garner a holistic understanding of electronic coupling for charge transfer reactions in organic electrodes.

This research elucidates a rescaling approach for calculating quantum energies associated with charge transfer reactions, significantly reducing the need for expensive Density Functional Theory (DFT) calculations. Our strategy involves estimating quantum electron-transfer (ET) energies through a comprehensive analysis of computationally economical classical MD data. Consequently, DFT calculations are now only necessary for rescaling the classical ET energies on a much smaller dataset. Notably, our research also highlights that quantum effects, such as charge delocalization, can provide additional stabilization following redox reactions, which is not accounted for in the classical ET energy distribution due to its inability to consider charge delocalization. Moreover, this work examines how variations in the electrolyte environment can alter the reorganization energy and, consequently, influence ET dynamics.