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Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4978411· OSTI ID:1347429
 [1];  [2];  [3]
  1. Rensselaer Polytechnic Inst., Troy, NY (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States); California Institute of Technology
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. Cornell Univ., Ithaca, NY (United States)
+ Show Author Affiliations
First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.
Research Organization:
California Inst. of Technology (CalTech), Pasadena, CA (United States); California Institute of Technology, Pasadena, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Organization:
USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; SC0001086; SC0004993
OSTI ID:
1347429
Alternate ID(s):
OSTI ID: 1348036
OSTI ID: 1467630
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Piecewise nonlinearity and capacitance in the joint density functional theory of extended interfaces journal April 2021
The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry journal August 2018
Simulation of Many-Electron Systems That Exchange Matter with the Environment: Simulation of Many-Electron Systems That Exchange Matter with the Environment journal August 2018
Continuum embeddings in condensed-matter simulations journal October 2018
Eliminating Trap‐States and Functionalizing Vacancies in 2D Semiconductors by Electrochemistry journal October 2019
Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media journal February 2019
Absolute band alignment at semiconductor-water interfaces using explicit and implicit descriptions for liquid water journal October 2019
Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution journal June 2019
Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis journal December 2019
The importance of grand-canonical quantum mechanical methods to describe the effect of electrode potential on the stability of intermediates involved in both electrochemical CO 2 reduction and hydrogen evolution journal January 2018
Energy landscape of the charge transfer reaction at the complex Li/SEI/electrolyte interface journal January 2019
Theoretical insight into the origin of the electrochemical promotion of ethylene oxidation on ruthenium oxide journal January 2019
Theory-guided materials design: two-dimensional MXenes in electro- and photocatalysis journal January 2019
Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations journal April 2018
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and electrode potentials journal January 2019
Grand canonical simulations of electrochemical interfaces in implicit solvation models journal January 2019
Exploring chemical speciation at electrified interfaces using detailed continuum models journal January 2019
Synergy between Fe and Ni in the optimal performance of (Ni,Fe)OOH catalysts for the oxygen evolution reaction journal May 2018

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