Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments

Electrochemical Insights into the Mechanisms of Proton Reduction by [Fe2(CO)6{μ‐SCH2N(R)CH2S}] Complexes Related to the [2Fe]H Subsite of [FeFe]Hydrogenase

“…Digital simulations (see Figure S3b in the Supporting Information) of the EC processes in Scheme 4 using DigiElch 3 [56] allow one to assign lower limits to the rate constant of the following step of k ! 8 10 2 s À1 and k !…”

“…Digital simulations: All the simulations were performed with DigiElch Special Build Version 3 (Build SB3.600). [56] Details of the procedure are given as Supporting Information.…”

“…Digital simulations [56] (see Supporting Information for full details of the procedure) based on the reactions in Scheme 5 were performed to check whether the transition from the process at À1.2 V to that at À1.4 V that is experimentally observed in the presence of HBF 4 could be reproduced by adjusting the equilibrium and rate constants of the protonation steps (K eq = K a (HA)/K a A C H T U N G T R E N N U N G (1-nH + ); n = 1-3). The CV of 1 was first simulated in the absence of acid, and then in the presence of acids with different pK a (pK a = 3 and 8.3) [39] with k = 3 s À1 as the rate constant for the release of H 2 from 1-2H (k exp = 3.0 AE 0.5 s…”

Splitting Water with Cobalt

“…The turnover frequency (apparent firstorder rate constant) can however be determined analytically in only very specific cases depending on the catalytic regime. [53,67,76] Numeric simulations of the cyclic voltammograms using DigiSim, DigiElch, [77][78][79][80][81][82] or related software may allow an estimation of the catalytic rate, but only if the catalytic mechanism is established. [48,51,52] As an example, the rate-determining step in H 2 evolution catalyzed by 12 ( Figure 9) is the protonation of a metal-hydride complex, and its constant was estimated to 1.35 10 4 mol À1 L s À1 .…”

Bistable Molecular Switches Based on Linkage Isomerization in Ruthenium Polypyridyl Complexes with a Ligand‐Bound Ambidentate Motif

“…[49,50] The half-wave potentials of the Ru III/II couples used for the simulations were determined as averages of the anodic and cathodic peak potentials of the quasireversible waves observed at sufficiently high scan rates where the isomerization reactions are essentially shut down. For the Ru III/II N 5 O couple these data were obtained after exhaustive bulk electrolysis or several seconds of equilibration (in case of the ultra micro electrodes) at oxidative potentials (with respect to the Ru III/II N 6 couple) that prepared the complex in the Ru III N 5 O form.…”