2012/05/31 by Kendra Letchworth‐Weaver, Kendra Letchworth-Weaver, T. A. Arias · 361 citations
Chemistry · Energy · Engineering · Physics and Astronomy · #Ab initio #Charge (physics) #Charge density #Chemical physics #Chemistry #Computational chemistry #Density functional theory #Electrocatalysts for Energy Conversion #Electrochemical Analysis and Applications #Electrochemistry #Electrode #Electrode potential #Electrolyte #Materials science #Molecular Junctions and Nanostructures #Physical chemistry #Physics #Quantum mechanics #Reference electrode #Standard electrode potential #Standard hydrogen electrode #Statistical physics #Thermodynamics #Work (physics) #cond-mat.mtrl-sci
paper · pdf · doi:10.1103/physrevb.86.075140
published in Physical Review B 86(7) (American Physical Society) · 18 pages, 5 figures. Initially presented at APS March Meeting 2010. Accepted for publication in Physical Review B on Jul. 27, 2012
arxiv created 2012/07/27 · openalex publication_date 2012/08/22 · arxiv updated 2015/06/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
This work explores the use of joint density functional theory, an extension of density functional theory for the ab initio description of electronic systems in thermodynamic equilibrium with a liquid environment, to describe electrochemical systems. After reviewing the physics of the underlying fundamental electrochemical concepts, we identify the mapping between commonly measured electrochemical observables and microscopically computable quantities within an, in principle, exact theoretical framework. We then introduce a simple, computationally efficient approximate functional which we find to be quite successful in capturing a priori basic electrochemical phenomena, including the capacitive Stern and diffusive Gouy-Chapman regions in the electrochemical double layer, quantitative values for interfacial capacitance, and electrochemical potentials of zero charge for a series of metals. We explore surface charging with applied potential and are able to place our ab initio results directly on the scale associated with the standard hydrogen electrode (SHE). Finally, we provide explicit details for implementation within standard density functional theory software packages at negligible computational cost over standard calculations carried out within vacuum environments.