II. Computational methods The computational methods employed for DFT analysis are detailed in Chapter 3. To calculate atomic charges and electron density maps, the Voronoi Deformation Density (VDD) method developed by Matthias Bickelhaupt et al.95 was utilized. Unlike other charge calculation methods, the VDD method does not rely on explicit basis functions. Instead, it determines the transfer of electronic density to or from specific atoms based on bond formation. This approach has been demonstrated to yield more chemically meaningful charges compared to other methods, such as Bader charges, which can result in extreme values and even exhibit ionic character in covalent bonds. III. Materials Anhydrous acetonitrile (99.8%), acetonitrile (ReagentPlus, 99%), dichloromethane (puriss p.a. ACS reagent 99.9%), diethyl ether (anhydrous, ACS reagent, 99.0%), bis(trifluoromethane)sulfonimide lithium salt (99%), silver trifluoromethanesulfonate (99%), acetonitrile-d3 (99.8 atom % D), dimethyl sulfoxide-d6 (99.9 atom % D), iodomethane (99.0%), 4,5-diphenylimidazole (98%), potassium hydride (30 wt% dispersion in mineral oil) and indene ((99%) were obtained from Sigma-Aldrich. Acetonitrile-d3 (99.8 atom % D) for electrolysis experiments was obtained from Acros Organics. 4,5-Dichloroimidazole (>97.0%) was obtained from TCI Europe N.V. 1,3-Dimethylimidazolium bis(trifluoromethylsulfonyl)imide (99%) was purchased from Iolitec Ionic Liquids Technologies GmbH. Milli-Q water was taken from a Milli-Q Advantage A10 Water Purification System, Millipore. 1,3-Dimethyl-4,5-dichloroimidazolium iodide was prepared according to a published procedure with some modifications96. 1,3,4,5-
RkJQdWJsaXNoZXIy MTk4NDMw