Solvation of anthraquinone and Tempo redox-active species in acetonitrile using a polarizable force field


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 structural properties of AQ, AQ$^{\bullet-}$, AQ$^{2-}$, TEMPO$^{\bullet}$ 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.


Supplementary material

Supplementary material
Fumi-Tosi combinations rules, details of DFT calculations, force field parameters, intermolecular RDFs for acetonitrile, AQ, AQ$^{\bullet-}$, AQ$^{2-}$, TEMPO$^{\bullet}$ and TEMPO$^{+}$, acetonitrile properties such as heat of vaporization, dielectric constant, diffusion coefficient and viscosity.