Over the last years, computational electrochemistry has made significant steps towards reproducing and explaining experimental electrochemical data and trends. The key for this success has been the development of continuum solvation techniques within density functional theory (DFT) program packages. These methods have enabled to simulate electrochemical processes in the correct grand-canonical ensemble, thus accounting for charge equilibration and adsorbate coupling to solvation and the electric double layer field. In this lecture, I will give a detailed overview over the key concepts and challenges of continuum solvation methods in all-electron and pseudo-potential based DFT packages. In addition, I then extend this methodological discussion to applications to electrochemistry for which I also highlight the key differences between the grand-canonical (constant potential) and canonical (constant charge) approaches. Finally, I give some short outlook into grand-canonical simulations of non-equilibrium systems, as well as the replacement of the continuum solvation with fully atomistic electrolyte models, such as QM/MM.
[1] - Ringe, S. et al., Chem. Rev. 2022, 122, 10777–10820.
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Financial Support
The Cooper Union for the Advancement of Science and Art is pleased to provide support for the 2024 VWSCC through a generous donation from Alan Fortier.
We thank Leibniz Institute for Catalysis (LIKAT) and CECAM for their support.
Virtual Winter School on Computational Chemistry