Some of the topics in computational electrochemistry that will be covered during the workshop are the following:
- Electron transfer, including new theoretical methodologies (Green’s functions, constrained DFT, …). We will discuss about new implementations of constrained DFT (CP2K, GPAW codes) and
their applicability to, for example, parametrize Marcus theory. We will also discuss the applicability of transport methodology, such as non-equilibrium Green’s function formalism (e.g., the
QuantumWise implementation), to be extended from the semiconductor/metal framework to the electrolyte/electrode framework.
- Solute/electrode interaction. We will look at the theoretical and computational description of molecular adsorption (inner sphere redox reactions), how the electrode morphology affects the
adsorption energies (e.g., different crystal facets), the role of electrode potential on adsorption, developments in transition state theory to explain catalytic properties of surfaces, and the ability
of new methodologies, such as machine learning, to efficiently optimize structures within the huge parameter space of molecular adsorption.
- Solvent/electrode interface. We will tackle the problem of accurately describing the electrical double layer under different electrode potentials and electrode morphologies. The need for and domain of applicability of different methodological frameworks (e.g., molecular dynamics vs. optimized geometries) will be discussed.
- Solvent effects. We will look at the effect of solvation sheets and solvation free energies on redox potentials for outer-sphere complexes. In particular, we will debate under which conditions simple
continuum solvation models are enough and under which conditions explicit solvation with atomistic resolution is required. QM/MM methodologies will be explored here, on how to accurately account
for the first solvation layers and incorporate the “bulk” solvent effects at a lower level of theory.
- Effect of pH and solute concentration. Some effects cannot be directly simulated due to the scales involved, these are for instance incorporation of pH values when the proton concentration is
lower than 1/100 or 1/1000 (which is the case for pH & 1). Indirect methods are therefore required to estimate pH effects on phase-stability and coexisting phases, compute Pourbaix diagrams, or
calculate pKa values. Such indirect strategies and their degree of accuracy will be discussed. How to compute the effect of solute concentration on the reaction kinetics will be another topic of
- Surface charge and potential tunability. We will explore the ability and limitations of different ways to incorporate surface charge and Fermi level changes into atomistic simulations of the
electrode/electrolyte interface. We will look at indirect methods of charging the surface such as counter-ions/adsorbates and novel direct methods such as modified pseudopotentials and Green’s
- Electrochemical scales. Direct and indirect ways to align computed redox levels with reference electrochemical scales will be discussed. For example, the applicability and reliability of “computational hydrogen electrode” (indirect) and the use of electrostatic potentials and vacuum offsets (direct) will be discussed.
- Multiscale approaches. We will look at how QM/MM and other methods to couple different length scales can be applied to study the electrode/electrolyte interface, to model the band bending
in semiconductor electrodes, etc.
- Non-aqueous electrochemistry, liquid/liquid interfaces and other exotic electrochemistry problems. Electrochemistry in solvents other than water (e.g., acetonitrile) and exotic electrochemical problems which need radically different approaches, such as water/organic solvent electrochemical interfaces, will also be discussed during the workshop.