Modeling Electrochemical Processes with Grand Canonical Treatment of Many-Body Perturbation Theory

Ziyang Wei, Florian Göltl, Stephan N. Steinmann, Philippe Sautet

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Electrocatalysis plays a key role in sustainable energy conversion and storage. It is critical to model the grand canonical treatment of electrons, which accounts for the electrochemical potential explicitly, at the atomic scale and understand these reactions at electrified interfaces. However, such a grand canonical treatment for electrocatalytic modeling is in practice restricted to a treatment of electronic structure with density functional theory, and more accurate methods are in many cases desirable. Here, we develop an original workflow combining the grand canonical treatment of electrons with many-body perturbation theory in its random phase approximation (RPA). Using the potential dependent adsorption of carbon monoxide on the copper (100) facet, we show that the grand canonical RPA energetics provide the correct on-top Cu geometry for CO at reducing potential. The match with experimental results is significantly improved compared to the functionals at the generalized gradient approximation level, which is the most commonly used approximation for electrochemical applications. We expect this development to pave the way to further electrochemical applications using RPA.

Original languageEnglish (US)
Pages (from-to)6079-6084
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume13
Issue number26
DOIs
StatePublished - Jul 7 2022
Externally publishedYes

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry

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