New Software for Simulation of Electrochemical Reaction Mechanisms of Any Complexity

Abstract

We introduce here our scientific software KISSA designed for automatic simulation of electrochemical reaction mechanisms of any complexity, including those leading to ECL emission at planar, (hemi)spherical and (hemi)cylindrical working electrodes (KISSA-1D) as well as at microelectrodes such as disk or band (KISSA-2D). Simulations are performed by KISSA using a novel approach [1, 2] developed by the authors which involves conformal coordinate transformations to overcome the numerical difficulties arising from diffusional propagation of species and automatic grid adaptation based on the detection of large kinetic terms to obtain accurate results for both concentrations and electrochemical currents even in the presence of steep concentration gradients. This approach allows for efficient resolution of all physicochemical and mathematical issues connected both with edge effects (nano- and microelectrodes) and considerable disparity of time and length scales of the underlying processes arising due to quickly changing electrode potential and/or extremely rapid homogeneous chemical reactions for any complex mechanisms. The software offers a possibility to take into account spontaneous natural convection which limits the extent of the diffusion layer and leads to the establishment of a steady state current even at macroelectrodes. Furthermore, this enables setting correct and thermodynamically consistent initial conditions within the stagnant layer when the system is pre-equilibrated at a given rest potential for a finite period of time [3]. The software also allows simulating complex adsorption dynamics, i.e., kinetics and chemical reactions involving surface-bound species [4, 5]. The programs offer convenient entry of a reaction mechanism and parameters and provide access to the computed dynamic spatial distributions of all important quantities such as currents and current densities, concentration distributions of all reactants, surface coverage of adsorbed species [4, 5] as well as ECL intensity [6] (if applicable) through a graphical user interface [7]. [1] C. Amatore, O.V. Klymenko, I. Svir, Electrochem. Commun. 12 (2010) 1170. [2] O.V. Klymenko, I. Svir, A. Oleinick, C. Amatore, ChemPhysChem 13 (2012) 845. [3] C. Amatore, O.V. Klymenko, I. Svir, Anal. Chem. 84 (2012) 2792. [4] O.V. Klymenko, I. Svir, C. Amatore, J. Electroanal. Chem. 688 (2013) 320. [5] O.V. Klymenko, I. Svir, C. Amatore, Molecular Physics, 112 (2014) 1273. [6] O.V. Klymenko, I. Svir, C. Amatore, ChemPhysChem, 14 (2013) 2237. [7] http://kissagroup.com/index.php/bibliography