Implicit self-consistent electrolyte model in plane-wave density-functional theory

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  • Kiran Mathew
    Department of Materials Science and Engineering, Cornell University 1 , Ithaca, New York 14853, USA
  • V. S. Chaitanya Kolluru
    Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA
  • Srinidhi Mula
    Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA
  • Stephan N. Steinmann
    University Lyon, Ecole Normale Supérieure de Lyon, CNRS, Université Lyon 1, Laboratoire de Chimie UMR 5182 4 , 46 allée d’Italie, F-69364 Lyon, France
  • Richard G. Hennig
    Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA

Abstract

<jats:p>The ab initio computational treatment of electrochemical systems requires an appropriate treatment of the solid/liquid interfaces. A fully quantum mechanical treatment of the interface is computationally demanding due to the large number of degrees of freedom involved. In this work, we develop a computationally efficient model where the electrode part of the interface is described at the density-functional theory (DFT) level, and the electrolyte part is represented through an implicit solvation model based on the Poisson-Boltzmann equation. We describe the implementation of the linearized Poisson-Boltzmann equation into the Vienna Ab initio Simulation Package, a widely used DFT code, followed by validation and benchmarking of the method. To demonstrate the utility of the implicit electrolyte model, we apply it to study the surface energy of Cu crystal facets in an aqueous electrolyte as a function of applied electric potential. We show that the applied potential enables the control of the shape of nanocrystals from an octahedral to a truncated octahedral morphology with increasing potential.</jats:p>

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