Approximating constant potential DFT with canonical DFT and electrostatic corrections
Publiceringsår
2023
Upphovspersoner
Domínguez-Flores, Fabiola; Melander, Marko M.
Abstrakt
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.
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Publikationstyp
Publikationsform
Artikel
Moderpublikationens typ
Tidning
Artikelstyp
En originalartikel
Målgrupp
VetenskapligKollegialt utvärderad
Kollegialt utvärderadUKM:s publikationstyp
A1 Originalartikel i en vetenskaplig tidskriftPublikationskanalens uppgifter
Journal
Förläggare
Volym
158
Nummer
14
Artikelnummer
144701
ISSN
Publikationsforum
Publikationsforumsnivå
1
Öppen tillgång
Öppen tillgänglighet i förläggarens tjänst
Nej
Parallellsparad
Ja
Övriga uppgifter
Vetenskapsområden
Fysik; Kemi
Nyckelord
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Publiceringsland
Förenta staterna (USA)
Förlagets internationalitet
Internationell
Språk
engelska
Internationell sampublikation
Nej
Sampublikation med ett företag
Nej
DOI
10.1063/5.0138197
Publikationen ingår i undervisnings- och kulturministeriets datainsamling
Ja