Oliviero Andreussi (now assistant professor at UNT, Denton)
Nicolas Hörmann (EPFL)
Francesco Nattino (EPFL)
Our focus on electrochemistry is twofold:
We develop multiscale continuum models to mimic the presence of electrolyte solutions in first-principles simulations. These models allow to bypass the computational and conceptual limitations that characterize fully-atomistic quantum simulations of electrochemical interfaces, while simultaneously enabling a realistic description of the solvation environment [1-4]. The developed continuum models are implemented in the open-source ENVIRON module for Quantum ESPRESSO.
We apply these combined quantum-continuum models to study chemisorption, vibrational frequencies and relative interface stability as a function of the applied potential. These simulations allow to predict and understand material and adsorbate properties such as Stark tuning, surface Pourbaix diagrams and equilibrium Wulff shapes (see e.g. [5,6]).
[1] O. Andreussi, I. Dabo and N. Marzari. Revised self-consistent continuum solvation in electronic structure calculations, J. Chem. Phys. 136, 064102 (2012)
[2] C. Dupont, O. Andreussi and N. Marzari. Self-consistent continuum solvation (SCCS): The case of charged systems, J. Chem. Phys. 139, 214110 (2013)
[3] O. Andreussi and N. Marzari. Electrostatics of solvated systems in periodic boundary conditions, Phys. Rev. B 90, 245101 (2014)
[4] G. Fisicaro, L. Genovese, O. Andreussi, S. Mandal, N.N. Nair, N. Marzari, and S. Goedecker. Soft-Sphere Continuum Solvation in Electronic-Structure Calculations, J. Chem. Theory Comput. 13, 3829 (2017)
[5] J. Huang, N. Hörmann, E. Oveisi, A. Loiudice, G.L. De Gregorio, O. Andreussi, N. Marzari, and R. Buonsanti. Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction, Nat. Commun. 9, 3117 (2018)
[6] Y. Katayama, F. Nattino, L. Giordano, J. Hwang, R. R. Rao, O. Andreussi, N. Marzari, and Y. Shao-Horn. An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates, J. Phys. Chem. C (published online 2018)
[7] F. Nattino, M. Truscott, N. Marzari, and O. Andreussi. Continuum models of the electrochemical diffuse layer in electronic-structure calculations, J. Chem. Phys. 150, 041722 (2019)
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