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Title: 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) | H 2O and Al(111) | H 2O 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 ( E F). 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:
 [1];  [2];  [3];  [3];  [4];  [3];  [2];  [2];  [5]
  1. Stanford Univ., Stanford, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Princeton Univ., Princeton, NJ (United States)
  4. Stanford Univ., Stanford, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1459652
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: 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. 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, and Norskov, Jens K. Fri . "Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer". United States. doi: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},
issn = {2041-1723},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {8}
}

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