Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations

We investigated the cathodic and anodic limits of six room-temperature ionic liquids (ILs) formed from a combination of two common cations, 1-butyl-3-methylimidazolium (BMIM) and N,N-propylmethylpyrrolidinium (P13), and three common anions, PF6, BF4, and bis(trifluoromethylsulfonyl)imide (TFSI), using an approach that combines molecular dynamics (MD) simulations and density functional theory (DFT) calculations. All interion interactions were taken into account by explicitly modeling the entire liquid structure using classical MD, followed by DFT computations of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies. The relative cathodic and anodic limits of BMIM PF6, BMIM BF4, BMIM TFSI, and P13 TFSI obtained from our approach are in fairly good agreement with existing experimental data. From our DFT calculations, we also obtained the cation- and anion-projected density of states (DOS), which provide information on the likely species contributing to reductiv...

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