Simulation framework rs@md consists of performing a classic MD simulation that is periodically interrupted in order to insert or remove molecular bonds according to the definitions of the involved reactions. The conditions for the insertion or removal of bonds can be subdivided into geometric and dynamic conditions. In the former the spatial proximity of the reactants is verified while the latter corresponds to the probability of a reaction to occur per unit time given that the first condition is met. The geometric conditions (depicted in Figure ) are derived from classic force field parameters and correspond to inter-molecular cut-off distances while the dynamic conditions are defined via the "gas-phase" energy difference between the initial state and the transition state of the reactive complex in accordance with transition state theory. The operation of bond rearrangement has previously been shown to involve non-trivial difficulties related with the smoothness of the resulting force field and an approach based on performing local relaxations of the product molecules af-ter each reaction has consequently been suggested. The consistency of this approach with respect to structural and dynamic system properties has been verified 15 by means of a comparison with AIMD simulations of dimerization of singly reduced EC radicals in solution to form dilithium butyl dicarbonate (Li 2 BDC). Similar approaches were used to include electrochemical charge-transfer reactions in an electrode/electrolyte interface leading to SEI formation and showed that a porous passivation layer developed within simulation-times of ∼ 10 ns. The present work focuses on the effect of elementary charge transfer rates on the effective formation rates. The force field used for the MD runs is OPLS-AA optimized for conformational and energetic properties of organic liquids and the CL&P force field for ionic liquids. The simulations were performed with the GROMACS-2019.3 version. The initial structures of the electrolyte were generated with the open-source software PACK-MOL. All results described above have been cross-validated using the methods described in Abbot & Hanke 13 using the COMPASSIII forcefield with systems constructed with the Materials Studio Amorphous cell module. Model system A three-dimensional frozen graphitic anode structure in contact with a carbonate electrolyte composed of lithium hexa-fluorophosphate (LiPF 6 ) salt dissolved in a pure EC solution is implemented as the baseline system. Throughout all simulations the initial electrolyte structures have been generated by randomly packing 140 LiPF 6 pairs and 1800 EC molecules within a rectangular cell of 3.5 × 3.5 × 17 [nm 3 ]. The ratio of salt to solvent molecules corresponds to the one molar reference value of the salt concentration. Previous work has established that most of the electrolyte decomposition products originate from the EC solvent molecule due to its high polarity and strong interaction with the electrode surface. Therefore this justifies the simplified choice of EC as the only solvent molecule in the reactive model. The implemented pathway consists of a sequence of fragmentation and dimerization reactions initiated by the electron transfer from the graphite electrode to the EC molecule. This mechanism is supported by ample evidence and numerous investiga-tions from both the experimental and theoretical communities. EC is not expected to be stable under standard operation conditions because the lowest unoccupied molecular orbital (LUMO) of EC was shown to lie below the Fermi level of lithiated graphite. The decomposition peak of EC is correspondingly observed around 1 V at the Li/Li + scale, while the voltage operation range of the graphite anode is close to 0.1 V . The decomposition products of the implemented pathway (Li 2 CO 3 and Li 2 EDC/Li 2 BDC) are also widely reported from characterization studies based on Fourier transform infrared-red spectroscopy (FTIR) as well as X-ray photo-electron spectroscopy (XPS). The pathway is summarized in Figure and the related details can be found in our former work. The slab model is depicted in Figure . The slab geometry is implemented by imposing periodic boundary conditions (PBC) along all three coordinates. The choice of PBC along the z-coordinate allows using the graphite structure as an effective wall from the two ends of the electrolyte phase. A negative electric charge of -1.25 × 10 -2 e is assigned to the carbon atoms at the graphite/electrolyte contact surface implying a total surface charge of -2 e homogeneously distributed over the 3.5 × 3.5 [nm 2 ] surface, and thus a charge density of σ = 3.1 µC cm 2 . This value implies a voltage difference in the order of ∼ 1 V between the electrode and the electrolyte if a charged infinite plane model is assumed for the potential drop between the electrode and the electrolyte. The excess surface charge is compensated with a uniform positive background to ensure electroneutrality. The restriction to a uniform fixed charge on the electrode is justified as the electrode response to local charge fluctuations is not expected to significantly affect the results . The cut-off scheme used for the MD-integration consists of the Verlet algorithm within a discretization time of 1 f s.