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
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- V. S. Chaitanya Kolluru
- Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA
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- Srinidhi Mula
- Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA
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- 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
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- Richard G. Hennig
- Department of Materials Science and Engineering, University of Florida 2 , Gainesville, Florida 32611, USA
抄録
<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>
収録刊行物
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- The Journal of Chemical Physics
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The Journal of Chemical Physics 151 (23), 234101-, 2019-12-16
AIP Publishing