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Ionic liquids generally display peculiar structural features that impact their physical properties, such as the formation of polar and apolar domains. Recently, ionic liquids functionalized with anthraquinone and TEMPO redox groups were shown to increase the energy storage performance of supercapacitors, but their structure has not yet been characterized. In this work, we use polarizable molecular dynamics to study the nanostructuration of such biredox ionic liquids. We show that TEMPO nitroxyl functions tend to aggregate, while the anthraquinone groups favor stacked arrangements. The latter eventually percolate through the whole liquid, which sheds some light on the mechanisms at play within biredox ionic liquid-based supercapacitors.

Electrochemistry is central to many applications, ranging from biology to energy science. Studies now involve a wide range of techniques, both experimental and theoretical. Modeling and simulations methods, such as density functional theory or molecular dynamics, provide key information on the structural and dynamic properties of the systems. Of particular importance are polarization effects of the electrode/electrolyte interface, which are difficult to simulate accurately. Here, we show how these electrostatic interactions are taken into account in the framework of the Ewald summation method. We discuss, in particular, the formal setup for calculations that enforce periodic boundary conditions in two directions, a geometry that more closely reflects the characteristics of typical electrolyte/electrode systems and presents some differences with respect to the more common case of periodic boundary conditions in three dimensions. These formal developments are implemented and tested in MetalWalls, a molecular dynamics software that captures the polarization of the electrolyte and allows the simulation of electrodes maintained at a constant potential. We also discuss the technical aspects involved in the calculation of two sets of coupled degrees of freedom, namely the induced dipoles and the electrode charges. We validate the implementation, first on simple systems, then on the well-known interface between graphite electrodes and a room-temperature ionic liquid. We finally illustrate the capabilities of MetalWalls by studying the adsorption of a complex functionalized electrolyte on a graphite electrode.

Quinones are redox active organic molecules that have been proposed as an alternative choice to metal-based materials in electrochemical energy storage devices. Functionalization allows one to fine tune not only their chemical stability but also the redox potential and kinetics of the electron transfer reaction. However, the reaction rate constant is not only determined by the redox species but also impacted by solvent effects. In this work, we show how the functionalization of benzoquinone with different functional groups impacts the solvent reorganization free energies of electron transfer half-reactions in acetonitrile. The use of molecular density functional theory, whose computational cost for studying the electron transfer reaction is considerably reduced compared to the state-of-the-art molecular dynamics simulations, enables us to perform a systematic study. We validate the method by comparing the predictions of the solvation shell structure and the free energy profiles for electron transfer reaction to the reference classical molecular dynamics simulations in the case of anthraquinone solvated in acetonitrile. We show that all the studied electron transfer half-reactions follow the Marcus theory, regardless of functional groups. Consequently, the solvent reorganization free energy decreases as the molecular size increases.

Redox-active molecules are of interest in many fields, such as medicine, catalysis, or energy storage. In particular, in supercapacitor applications, they can be grafted to ionic liquids to form so-called biredox ionic liquids. To completely understand the structural and transport properties of such systems, an insight at the molecular scale is often required, but few force fields are developed ad hoc for these molecules. Moreover, they do not include polarization effects, which can lead to inaccurate solvation and dynamical properties. In this work, we developed polarizable force fields for redox-active species anthraquinone (AQ) and 2,2,6,6-tetra-methylpiperidinyl-1-oxyl (TEMPO) in their oxidized and reduced states as well as for acetonitrile. We validate the structural properties of AQ, AQ •- , AQ 2- , TEMPO • , and TEMPO + in acetonitrile against density functional theory-based molecular dynamics simulations and we study the solvation of these redox molecules in acetonitrile. This work is a first step toward the characterization of the role played by AQ and TEMPO in electrochemical and catalytic devices.

A dithienylethene (DTE) photochromic compound functionalized by ureidopyrimidinone (UPy) quadruple hydrogen bonding blocks was synthesized by Takeshita and coworkers [Takeshita et al., Chem. Commun., 2005, 761] in order to form a light-responsive supramolecular self-assembling system. In solution, the formation of supramolecular assemblies was only observed for one DTE isomer, namely the closed-form isomer. To rationalize this experimental finding, with the help of Molecular Dynamics (MD) and (time-dependent) DFT calculations, the behaviour of open-form and closed-form monomers, dimers, hexamers and π-stacked dimers in solution is investigated. Our simulations show that, for the open-form oligomers, the progression of the supramolecular assembly is hindered due to (i) the possible formation of a very stable cyclic dimer for the open-form parallel isomer, (ii) the relative flexibility of the open-form oligomers compared to their closed-form counterparts, and (iii) the possible existence of π-stacked dimers that constitute bottlenecks blocking the progression of the supramolecular self-assembly.