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PreprintCC BYChemRxiv

The pH effect in hydrogen evolution is a consequence of creating a solvated hydroxide ion

  • Samuel A. Olusegun1,2
  • Salem Rice1,2
  • Danielle Getz3,4
  • Veena S. Chauhan1,2
  • Luis H.Z. Feistel1,2
  • Shaama M. Sharada5,6,7
  • Linsey C. Seitz3,4
  • Joseph A. Gauthier1,2
7 affiliations
  1. 1Department of Chemical Engineering
  2. 2Texas Tech University
  3. 3Department of Chemical and Biological Engineering
  4. 4Northwestern University
  5. 5Mork Family Department of Chemical Engineering and Materials Science
  6. 6University of Southern California
  7. 7Department of Chemistry
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Abstract

The hydrogen evolution reaction is orders of magnitude faster in acid than in base on the same electrode, a pH effect that first-principles calculations have not quantitatively reproduced. We trace this failure to the treatment of the ions: standard density functionals with standard solvation treatments undersolvate hydroxide–the ionic product of alkaline hydrogen evolution–by more than 1 eV against experiment and coupled cluster benchmarks, an error that tracks the functional’s self-interaction error. A screened hybrid functional with reduced self-interaction error yields Au(111) Volmer barriers whose acidalkaline difference falls within the measured range of onset-potential separations, whereas semi-local functionals predict zero to three times the measured value. Quantitative computational electrocatalysis therefore demands functionals benchmarked jointly against ion solvation thermochemistry and molecule-surface energetics.

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Cite

BibTeXRIS
BibTeX
@misc{olusegun2026effect,
  title = {{The pH effect in hydrogen evolution is a consequence of creating a solvated hydroxide ion}},
  author = {Samuel A. Olusegun and Salem Rice and Danielle Getz and Veena S. Chauhan and Luis H.Z. Feistel and Shaama M. Sharada and Linsey C. Seitz and Joseph A. Gauthier},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15007494/v2},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007494/v2},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - The pH effect in hydrogen evolution is a consequence of creating a solvated hydroxide ion
AU  - Samuel A. Olusegun
AU  - Salem Rice
AU  - Danielle Getz
AU  - Veena S. Chauhan
AU  - Luis H.Z. Feistel
AU  - Shaama M. Sharada
AU  - Linsey C. Seitz
AU  - Joseph A. Gauthier
PY  - 2026
DA  - 2026/10/15
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15007494/v2
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007494/v2
AB  - The hydrogen evolution reaction is orders of magnitude faster in acid than in base on the same electrode, a pH effect that first-principles calculations have not quantitatively reproduced. We trace this failure to the treatment of the ions: standard density functionals with standard solvation treatments undersolvate hydroxide–the ionic product of alkaline hydrogen evolution–by more than 1 eV against experiment and coupled cluster benchmarks, an error that tracks the functional’s self-interaction error. A screened hybrid functional with reduced self-interaction error yields Au(111) Volmer barriers whose acidalkaline difference falls within the measured range of onset-potential separations, whereas semi-local functionals predict zero to three times the measured value. Quantitative computational electrocatalysis therefore demands functionals benchmarked jointly against ion solvation thermochemistry and molecule-surface energetics.
ER  -