Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer
Abstract
A detailed atomic-scale description of the electrochemical interface is essential to the understanding of electrochemical energy transformations. In this work, we investigate the charge of solvated protons at the Pt(111) | H2O and Al(111) | H2O interfaces. Using semi-local density functional theory as well as hybrid functionals and embedded correlated wavefunction methods as higher-level benchmarks, we show that the effective charge of a solvated proton in the electrochemical double layer or outer Helmholtz plane at all levels of theory is fractional, when the solvated proton and solvent band edges are aligned correctly with the Fermi level of the metal (EF). In conclusion, the observed fractional charge in the absence of frontier band mis-alignment arises from a significant overlap between the proton and the electron density from the metal surface, and results in an energetic difference between protons in bulk solution and those in the outer Helmholtz plane.
- Authors:
-
- Stanford Univ., Stanford, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Princeton Univ., Princeton, NJ (United States)
- Stanford Univ., Stanford, CA (United States)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1459652
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Chen, Leanne D., Bajdich, Michal, Martirez, J. Mark, Krauter, Caroline M., Gauthier, Joseph H., Carter, Emily A., Luntz, Alan C., Chan, Karen, and Norskov, Jens K. Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer. United States: N. p., 2018.
Web. doi:10.1038/s41467-018-05511-y.
Chen, Leanne D., Bajdich, Michal, Martirez, J. Mark, Krauter, Caroline M., Gauthier, Joseph H., Carter, Emily A., Luntz, Alan C., Chan, Karen, & Norskov, Jens K. Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer. United States. https://doi.org/10.1038/s41467-018-05511-y
Chen, Leanne D., Bajdich, Michal, Martirez, J. Mark, Krauter, Caroline M., Gauthier, Joseph H., Carter, Emily A., Luntz, Alan C., Chan, Karen, and Norskov, Jens K. Fri .
"Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer". United States. https://doi.org/10.1038/s41467-018-05511-y. https://www.osti.gov/servlets/purl/1459652.
@article{osti_1459652,
title = {Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer},
author = {Chen, Leanne D. and Bajdich, Michal and Martirez, J. Mark and Krauter, Caroline M. and Gauthier, Joseph H. and Carter, Emily A. and Luntz, Alan C. and Chan, Karen and Norskov, Jens K.},
abstractNote = {A detailed atomic-scale description of the electrochemical interface is essential to the understanding of electrochemical energy transformations. In this work, we investigate the charge of solvated protons at the Pt(111) | H2O and Al(111) | H2O interfaces. Using semi-local density functional theory as well as hybrid functionals and embedded correlated wavefunction methods as higher-level benchmarks, we show that the effective charge of a solvated proton in the electrochemical double layer or outer Helmholtz plane at all levels of theory is fractional, when the solvated proton and solvent band edges are aligned correctly with the Fermi level of the metal (EF). In conclusion, the observed fractional charge in the absence of frontier band mis-alignment arises from a significant overlap between the proton and the electron density from the metal surface, and results in an energetic difference between protons in bulk solution and those in the outer Helmholtz plane.},
doi = {10.1038/s41467-018-05511-y},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Fri Aug 10 00:00:00 EDT 2018},
month = {Fri Aug 10 00:00:00 EDT 2018}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Atomistic Mechanisms Underlying Selectivities in C 1 and C 2 Products from Electrochemical Reduction of CO on Cu(111)
journal, December 2016
- Xiao, Hai; Cheng, Tao; Goddard, William A.
- Journal of the American Chemical Society, Vol. 139, Issue 1
Quantum mechanical embedding theory based on a unique embedding potential
journal, April 2011
- Huang, Chen; Pavone, Michele; Carter, Emily A.
- The Journal of Chemical Physics, Vol. 134, Issue 15
Fractional charge perspective on the band gap in density-functional theory
journal, March 2008
- Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
- Physical Review B, Vol. 77, Issue 11
Water Structures at Metal Electrodes Studied by Ab Initio Molecular Dynamics Simulations
journal, January 2014
- Groß, Axel; Gossenberger, Florian; Lin, Xiaohang
- Journal of The Electrochemical Society, Vol. 161, Issue 8
Challenges in the first-principles description of reactions in electrocatalysis
journal, May 2011
- Schnur, Sebastian; Groß, Axel
- Catalysis Today, Vol. 165, Issue 1
Structure of water layers on hydrogen-covered Pt electrodes
journal, March 2013
- Roman, Tanglaw; Groß, Axel
- Catalysis Today, Vol. 202
The complete active space SCF method in a fock-matrix-based super-CI formulation
journal, March 1980
- Roos, Björn O.
- International Journal of Quantum Chemistry, Vol. 18, Issue S14
A grid-based Bader analysis algorithm without lattice bias
journal, January 2009
- Tang, W.; Sanville, E.; Henkelman, G.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
On the prediction of band gaps from hybrid functional theory
journal, July 2001
- Muscat, J.; Wander, A.; Harrison, N. M.
- Chemical Physics Letters, Vol. 342, Issue 3-4
Standard hydrogen electrode and potential of zero charge in density functional calculations
journal, September 2011
- Tripkovic, Vladimir; Björketun, Mårten E.; Skúlason, Egill
- Physical Review B, Vol. 84, Issue 11
Assessing a First-Principles Model of an Electrochemical Interface by Comparison with Experiment
journal, January 2016
- Steinmann, Stephan N.; Sautet, Philippe
- The Journal of Physical Chemistry C, Vol. 120, Issue 10
Structure and Bonding of Water on Pt(111)
journal, December 2002
- Ogasawara, H.; Brena, B.; Nordlund, D.
- Physical Review Letters, Vol. 89, Issue 27
Origin of the Energy Barrier to Chemical Reactions of on Al(111): Evidence for Charge Transfer, Not Spin Selection
journal, November 2012
- Libisch, Florian; Huang, Chen; Liao, Peilin
- Physical Review Letters, Vol. 109, Issue 19
Modeling the electrified solid–liquid interface
journal, November 2008
- Rossmeisl, Jan; Skúlason, Egill; Björketun, Mårten E.
- Chemical Physics Letters, Vol. 466, Issue 1-3
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989
- Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 90, Issue 2
Full atomistic reaction mechanism with kinetics for CO reduction on Cu(100) from ab initio molecular dynamics free-energy calculations at 298 K
journal, February 2017
- Cheng, Tao; Xiao, Hai; Goddard, William A.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 8
Density-functional theory of the band gap
journal, September 1985
- Sham, L. J.; Schlüter, M.
- Physical Review B, Vol. 32, Issue 6
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
The work function of the elements and its periodicity
journal, November 1977
- Michaelson, Herbert B.
- Journal of Applied Physics, Vol. 48, Issue 11
Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals
journal, December 2015
- Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo
- The Journal of Chemical Physics, Vol. 143, Issue 24
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Structural and electronic properties of aqueous NaCl solutions from ab initio molecular dynamics simulations with hybrid density functionals
journal, June 2014
- Gaiduk, Alex P.; Zhang, Cui; Gygi, François
- Chemical Physics Letters, Vol. 604
Dipole correction for surface supercell calculations
journal, May 1999
- Bengtsson, Lennart
- Physical Review B, Vol. 59, Issue 19
First-principles study of the water structure on flat and stepped gold surfaces
journal, June 2012
- Lin, Xiaohang; Groß, Axel
- Surface Science, Vol. 606, Issue 11-12
A set of d-polarization functions for pseudo-potential basis sets of the main group elements AlBi and f-type polarization functions for Zn, Cd, Hg
journal, June 1993
- Höllwarth, A.; Böhme, M.; Dapprich, S.
- Chemical Physics Letters, Vol. 208, Issue 3-4
The partial charge transfer
journal, May 2014
- Schmickler, Wolfgang; Guidelli, Rolando
- Electrochimica Acta, Vol. 127
The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule
journal, February 1981
- Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders
- The Journal of Chemical Physics, Vol. 74, Issue 4
Insights into Current Limitations of Density Functional Theory
journal, August 2008
- Cohen, A. J.; Mori-Sanchez, P.; Yang, W.
- Science, Vol. 321, Issue 5890
First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach
journal, March 2006
- Otani, M.; Sugino, O.
- Physical Review B, Vol. 73, Issue 11
Physical Content of the Exact Kohn-Sham Orbital Energies: Band Gaps and Derivative Discontinuities
journal, November 1983
- Perdew, John P.; Levy, Mel
- Physical Review Letters, Vol. 51, Issue 20
Electrostatics of solvated systems in periodic boundary conditions
journal, December 2014
- Andreussi, Oliviero; Marzari, Nicola
- Physical Review B, Vol. 90, Issue 24
Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities
journal, May 2013
- Jhong, Huei-Ru “Molly”; Ma, Sichao; Kenis, Paul JA
- Current Opinion in Chemical Engineering, Vol. 2, Issue 2
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014
- Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- The Journal of Chemical Physics, Vol. 140, Issue 8
Avoiding pitfalls in the modeling of electrochemical interfaces
journal, January 2013
- Björketun, Mårten E.; Zeng, ZhenHua; Ahmed, Rizwan
- Chemical Physics Letters, Vol. 555
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980
- Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M.
- Chemical Physics, Vol. 48, Issue 2
The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO 2 (110) Surface
journal, December 2016
- Ping, Yuan; Nielsen, Robert J.; Goddard, William A.
- Journal of the American Chemical Society, Vol. 139, Issue 1
The ionization potential of aqueous hydroxide computed using many-body perturbation theory
journal, July 2014
- Opalka, Daniel; Pham, Tuan Anh; Sprik, Michiel
- The Journal of Chemical Physics, Vol. 141, Issue 3
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Embedded Correlated Wavefunction Schemes: Theory and Applications
journal, May 2014
- Libisch, Florian; Huang, Chen; Carter, Emily A.
- Accounts of Chemical Research, Vol. 47, Issue 9
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Monte Carlo, density functional theory, and Poisson–Boltzmann theory study of the structure of an electrolyte near an electrode
journal, April 2002
- Boda, Dezsö; Fawcett, W. Ronald; Henderson, Douglas
- The Journal of Chemical Physics, Vol. 116, Issue 16
Quantifying the effects of the self-interaction error in DFT: When do the delocalized states appear?
journal, June 2005
- Lundberg, Marcus; Siegbahn, Per E. M.
- The Journal of Chemical Physics, Vol. 122, Issue 22
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Electrochemical Barriers Made Simple
journal, June 2015
- Chan, Karen; Nørskov, Jens K.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 14
The path towards sustainable energy
journal, December 2016
- Chu, Steven; Cui, Yi; Liu, Nian
- Nature Materials, Vol. 16, Issue 1
A directCI method with a multiconfigurational reference state
journal, March 1980
- Roos, Bj�rn O.; Siegbahn, Per E. M.
- International Journal of Quantum Chemistry, Vol. 17, Issue 3
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990
- Vanderbilt, David
- Physical Review B, Vol. 41, Issue 11, p. 7892-7895
Revised self-consistent continuum solvation in electronic-structure calculations
journal, February 2012
- Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola
- The Journal of Chemical Physics, Vol. 136, Issue 6
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
journal, January 1985
- Wadt, Willard R.; Hay, P. Jeffrey
- The Journal of Chemical Physics, Vol. 82, Issue 1
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis
journal, September 2010
- Zope, B. N.; Hibbitts, D. D.; Neurock, M.
- Science, Vol. 330, Issue 6000
Density functional theory simulations of water–metal interfaces: waltzing waters, a novel 2D ice phase, and more
journal, September 2006
- Michaelides, A.
- Applied Physics A, Vol. 85, Issue 4
Excited-State N 2 Dissociation Pathway on Fe-Functionalized Au
journal, March 2017
- Martirez, John Mark P.; Carter, Emily A.
- Journal of the American Chemical Society, Vol. 139, Issue 12
Alignment of electronic energy levels at electrochemical interfaces
journal, January 2012
- Cheng, Jun; Sprik, Michiel
- Physical Chemistry Chemical Physics, Vol. 14, Issue 32
Heterometallic antenna−reactor complexes for photocatalysis
journal, July 2016
- Swearer, Dayne F.; Zhao, Hangqi; Zhou, Linan
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 32
Properties of metal–water interfaces studied from first principles
journal, December 2009
- Schnur, Sebastian; Groß, Axel
- New Journal of Physics, Vol. 11, Issue 12
Solvated protons in density functional theory—A few examples
journal, August 2013
- Quaino, P.; Luque, N. B.; Soldano, G.
- Electrochimica Acta, Vol. 105
Joint density functional theory of the electrode-electrolyte interface: Application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge
journal, August 2012
- Letchworth-Weaver, Kendra; Arias, T. A.
- Physical Review B, Vol. 86, Issue 7
First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure
journal, April 2006
- Taylor, Christopher D.; Wasileski, Sally A.; Filhol, Jean-Sebastien
- Physical Review B, Vol. 73, Issue 16
Potential Dependence of Electrochemical Barriers from ab Initio Calculations
journal, April 2016
- Chan, Karen; Nørskov, Jens K.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
Identification of Possible Pathways for C–C Bond Formation during Electrochemical Reduction of CO 2 : New Theoretical Insights from an Improved Electrochemical Model
journal, April 2016
- Goodpaster, Jason D.; Bell, Alexis T.; Head-Gordon, Martin
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 8
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
An ultrasensitive molybdenum-based double-heterojunction phototransistor
text, January 2021
- , Feng; , Liu; , Zhu
- Zenodo
Heterometallic antenna-reactor complexes for photocatalysis.
text, January 2016
- Swearer, Dayne F.; Zhao, Hangqi; Zhou, Linan
- Apollo - University of Cambridge Repository
Fractional charge perspective on the band-gap in density-functional theory
text, January 2007
- Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
- arXiv
Electrostatics of solvated systems in periodic boundary conditions
text, January 2014
- Andreussi, Oliviero; Marzari, Nicola
- arXiv
Challenges in the first-principles description of reactions in electrocatalysis
journal, May 2011
- Schnur, Sebastian; Groß, Axel
- Catalysis Today, Vol. 165, Issue 1
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Monte Carlo, density functional theory, and Poisson–Boltzmann theory study of the structure of an electrolyte near an electrode
journal, April 2002
- Boda, Dezsö; Fawcett, W. Ronald; Henderson, Douglas
- The Journal of Chemical Physics, Vol. 116, Issue 16
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Revised self-consistent continuum solvation in electronic-structure calculations
journal, February 2012
- Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola
- The Journal of Chemical Physics, Vol. 136, Issue 6
Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals
journal, December 2015
- Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo
- The Journal of Chemical Physics, Vol. 143, Issue 24
A grid-based Bader analysis algorithm without lattice bias
journal, January 2009
- Tang, W.; Sanville, E.; Henkelman, G.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis
journal, September 2010
- Zope, B. N.; Hibbitts, D. D.; Neurock, M.
- Science, Vol. 330, Issue 6000
Properties of metal-water interfaces studied from first principles
text, January 2009
- Schnur, Sebastian; Groß, Axel
- Universität Ulm
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
text, January 2013
- Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- arXiv
Electrostatics of solvated systems in periodic boundary conditions
text, January 2014
- Andreussi, Oliviero; Marzari, Nicola
- arXiv
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- The Journal of Chemical Physics, Vol. 150, Issue 4
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