From absolute potentials to a generalized computational standard hydrogen electrode for aqueous and non-aqueous solvents

Michael Busch*, Elisabet Ahlberg, Kari Laasonen

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

We describe a simple and efficient procedure to compute a conversion factor for the absolute potential of the standard hydrogen electrode in water to any other solvent. In contrast to earlier methods our procedure only requires the pK(a) of an arbitrary acid in water and few simple quantum chemical calculations as input. Thus, it is not affected adversely by experimental shortcomings related to measurements in non-aqueous solvents. By combining this conversion factor with the absolute potential in water, the absolute potential in the solvent of interest is obtained. Based on this procedure a new generalized computational standard hydrogen electrode for the computation of electron transfer and proton-coupled electron transfer potentials in non-aqueous solvents and ionic liquids is developed. This enables for the first time the reliable prediction of redox potentials in any solvent. The method is tested through calculation of absolute potentials in 36 solvents. Using the Kamlet-Taft linear solvation energy model we find that the relative absolute potentials consistently increase with decreasing polarisability and decreasing hydrogen bonding ability. For protic solvents good agreement with literature is observed while significant deviations are found for aprotic solvents. The obtained conversion factors are independent of the quantum chemical method, while minor differences are observed between solvation models. This does, however, not affect the global trends.

Original languageEnglish
Pages (from-to)11727-11737
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number20
Early online date4 May 2021
DOIs
Publication statusPublished - 28 May 2021
MoE publication typeA1 Journal article-refereed

Keywords

  • CHLORINE EVOLUTION REACTION
  • SOLVATION FREE-ENERGIES
  • REDOX POTENTIALS
  • OXYGEN EVOLUTION
  • WATER CLUSTERS
  • 1ST PRINCIPLES
  • IONIC LIQUIDS
  • WORK FUNCTION
  • REDUCTION
  • OXIDATION

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