Intermolecular electron-self exchange kinetics measured by electron paramagnetic resonance-linebroadening effects: useful rate constants for the application of Marcus theory

ESR and ENDOR investigations of the degenerate electron exchange reactions of various viologens in solution. Solvent dynamical effects

“…The concentration of the diamagnetic parent molecules was varied between 0 and 5.10 -2 M, giving rise to significant alternating line width effects that cover the whole range from the slow to the fast exchange limit [31]. For each solvent and temperature the ESR spectra were studied at no less than five concentrations of the diamagnetic precursor in order to extract the first-order rate constants.…”

Uncovering the Shuttle Effect in Organic Batteries and Counter‐Strategies Thereof: A Case Study of the N,N′‐Dimethylphenazine Cathode

“…Although these results do not directly prove the shuttle current to be carried by DMPZ/DMPZ .+ pairs within battery cells, this shuttling mechanism is supported by previous reports that describe electric conductivity based on the electron self‐exchange reaction, giving credence to our proposed shuttling mechanism as illustrated in Figure e where the shuttle current is carried by electron hopping between the active materials dissolved in the electrolyte. In fact, based on some reported precedents, the rate constant for electron self‐exchange for various organic couples in a range of solvents (viscous or non‐viscous, ionic and non‐ionic) is rather similar at an order of magnitude of around 10 8 m −1 s −1 . Based on a previously reported model together with this electron self‐exchange rate constant, our crude estimate of the shuttle current is calculated to be around 25 mA (see the section in the supporting information entitled “Modelling shuttle current based on self‐exchange”).…”

ESR Spectroscopy of Nitroxides: Kinetics and Dynamics of Exchange Reactins

“…This marks the beginning of the fast region, where a further increase in the exchange rate leads to narrowing of the single line. A chemical reaction corresponding to this illustration could, for example, be an exchange reaction like the one shown in equation (1), where the forms a and b are interpreted as being molecules having different nuclear spin configurations. …”

“…Such systems may still be in the intermediate region and equation (5) does not hold. In an effort to decide if a given system is indeed exhibiting fast exchange, the following relation may be used [1].…”