A1 Journal article (refereed)
Approximating constant potential DFT with canonical DFT and electrostatic corrections (2023)

Domínguez-Flores, F., & Melander, M. M. (2023). Approximating constant potential DFT with canonical DFT and electrostatic corrections. Journal of Chemical Physics, 158(14), Article 144701. https://doi.org/10.1063/5.0138197

JYU authors or editors

Publication details

All authors or editorsDomínguez-Flores, Fabiola; Melander, Marko M.

Journal or seriesJournal of Chemical Physics



Publication year2023

Publication date14/04/2023


Issue number14

Article number144701

PublisherAIP Publishing

Publication countryUnited States

Publication languageEnglish


Publication open accessNot open

Publication channel open access

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/88186


The complexity of electrochemical interfaces has led to the development of several approximate density functional theory (DFT)-based schemes to study reaction thermodynamics and kinetics as a function of electrode potential. While fixed electrode potential conditions can be simulated with grand canonical ensemble DFT (GCE-DFT), various electrostatic corrections on canonical, constant charge DFT are often applied instead. In this work, we present a systematic derivation and analysis of the different electrostatic corrections on canonical DFT to understand their physical validity, implicit assumptions, and scope of applicability. Our work highlights the need to carefully address the suitability of a given model for the problem under study, especially if physical or chemical insight in addition to reaction energetics is sought. In particular, we analytically show that the different corrections cannot differentiate between electrostatic interactions and covalent or charge-transfer interactions. By numerically testing different models for CO2 adsorption on a single-atom catalyst as a function of the electrode potential, we further show that computed capacitances, dipole moments, and the obtained physical insight depend sensitively on the chosen approximation. These features limit the scope, generality, and physical insight of these corrective schemes despite their proven practicality for specific systems and energetics. Finally, we suggest guidelines for choosing different electrostatic corrections and propose the use of conceptual DFT to develop more general approximations for electrochemical interfaces and reactions using canonical DFT.

Keywordselectrochemistryelectrostaticsdensity functional theoryadsorptionelectrolyteselectrodesgraphene

Free keywordsthermodynamic functions; graphene; electrolytes; electrostatics; electrochemical potential; statistical thermodynamics; electrochemistry; density functional theory; adsorption

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Ministry reportingYes

Reporting Year2023

JUFO rating1

Last updated on 2024-15-06 at 22:07