Importance of the gas-phase error correction for O2 when using DFT to model the oxygen reduction and evolution reactions

Elizabeth Sargeant; Francesc Illas; Paramaconi Rodriguez; Federico  Calle-Vallejo

doi:10.1016/j.jelechem.2021.115178

Importance of the gas-phase error correction for O₂ when using DFT to model the oxygen reduction and evolution reactions

Elizabeth Sargeant, Francesc Illas, Paramaconi Rodriguez, Federico Calle-Vallejo

Chemistry

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Abstract

DFT modelling of the oxygen reduction and evolution reactions (ORR and OER) habitually makes use of semiempirical corrections to oxygen in the gas phase. Although such corrections are tacit in the model, they should not be overlooked. In this article, we calculate the errors in the total energy of oxygen for commonly used exchange-correlation functionals, PW91, RPBE, PBE, and BEEF-vdW, to show that, for all functionals tested, the error is at least 0.3 eV. We discuss the impact this sizeable error in oxygen has on the modelling of the ORR and the OER. The error due to oxygen affects not only the overall equilibrium potential of the reaction, but also the energies of individual mechanistic steps. This illustrates that understanding the reasoning behind the semiempirical corrections for oxygen is important for researching new catalysts which may have different potential limiting steps.

Original language	English
Article number	115178
Number of pages	7
Journal	Journal of Electroanalytical Chemistry
Volume	896
DOIs	https://doi.org/10.1016/j.jelechem.2021.115178
Publication status	Published - 1 Sept 2021

Bibliographical note

Funding Information:
This work was performed under the project HPC-EUROPA3 (INFRAIA-2016-1-730897) with the support of the EC Research Innovation Action under the H2020 program and the computer resources and technical support provided by the Barcelona Supercomputing Center (BCN). We acknowledge the financial support from Spanish MICIUN through RTI2018- 095460-B-I00 and María de Maeztu MDM-2017-0767 grants and, in part, from Generalitat de Catalunya, grant 2017SGR13. F.C.-V. thanks MICIUN for a Ramón y Cajal research contract (RYC-2015-18996), and F.I. acknowledges additional support from the 2015 ICREA Academia Award for Excellence in University Research. E.S. acknowledges the University of Birmingham and the EPSRC Centre for Doctoral Training in Carbon Capture and Storage and Cleaner Fossil Energy for financial support through Ph.D. scholarships at the School of Chemistry at the University of Birmingham. P.R. and E.S. acknowledge the University of Birmingham for financial support.

Publisher Copyright:
© 2021 Elsevier B.V.

Keywords

Oxygen reduction reaction
Oxygen evolution reaction
Equilibrium potential
Gas phase errors
Gas phase correction
DFT

ASJC Scopus subject areas

Analytical Chemistry
Chemical Engineering(all)
Electrochemistry

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Cite this

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title = "Importance of the gas-phase error correction for O2 when using DFT to model the oxygen reduction and evolution reactions",

abstract = "DFT modelling of the oxygen reduction and evolution reactions (ORR and OER) habitually makes use of semiempirical corrections to oxygen in the gas phase. Although such corrections are tacit in the model, they should not be overlooked. In this article, we calculate the errors in the total energy of oxygen for commonly used exchange-correlation functionals, PW91, RPBE, PBE, and BEEF-vdW, to show that, for all functionals tested, the error is at least 0.3 eV. We discuss the impact this sizeable error in oxygen has on the modelling of the ORR and the OER. The error due to oxygen affects not only the overall equilibrium potential of the reaction, but also the energies of individual mechanistic steps. This illustrates that understanding the reasoning behind the semiempirical corrections for oxygen is important for researching new catalysts which may have different potential limiting steps.",

keywords = "Oxygen reduction reaction, Oxygen evolution reaction, Equilibrium potential, Gas phase errors, Gas phase correction, DFT",

author = "Elizabeth Sargeant and Francesc Illas and Paramaconi Rodriguez and Federico Calle-Vallejo",

note = "Funding Information: This work was performed under the project HPC-EUROPA3 (INFRAIA-2016-1-730897) with the support of the EC Research Innovation Action under the H2020 program and the computer resources and technical support provided by the Barcelona Supercomputing Center (BCN). We acknowledge the financial support from Spanish MICIUN through RTI2018- 095460-B-I00 and Mar{\'i}a de Maeztu MDM-2017-0767 grants and, in part, from Generalitat de Catalunya, grant 2017SGR13. F.C.-V. thanks MICIUN for a Ram{\'o}n y Cajal research contract (RYC-2015-18996), and F.I. acknowledges additional support from the 2015 ICREA Academia Award for Excellence in University Research. E.S. acknowledges the University of Birmingham and the EPSRC Centre for Doctoral Training in Carbon Capture and Storage and Cleaner Fossil Energy for financial support through Ph.D. scholarships at the School of Chemistry at the University of Birmingham. P.R. and E.S. acknowledge the University of Birmingham for financial support. Publisher Copyright: {\textcopyright} 2021 Elsevier B.V.",

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AU - Calle-Vallejo, Federico

N1 - Funding Information: This work was performed under the project HPC-EUROPA3 (INFRAIA-2016-1-730897) with the support of the EC Research Innovation Action under the H2020 program and the computer resources and technical support provided by the Barcelona Supercomputing Center (BCN). We acknowledge the financial support from Spanish MICIUN through RTI2018- 095460-B-I00 and María de Maeztu MDM-2017-0767 grants and, in part, from Generalitat de Catalunya, grant 2017SGR13. F.C.-V. thanks MICIUN for a Ramón y Cajal research contract (RYC-2015-18996), and F.I. acknowledges additional support from the 2015 ICREA Academia Award for Excellence in University Research. E.S. acknowledges the University of Birmingham and the EPSRC Centre for Doctoral Training in Carbon Capture and Storage and Cleaner Fossil Energy for financial support through Ph.D. scholarships at the School of Chemistry at the University of Birmingham. P.R. and E.S. acknowledge the University of Birmingham for financial support. Publisher Copyright: © 2021 Elsevier B.V.

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N2 - DFT modelling of the oxygen reduction and evolution reactions (ORR and OER) habitually makes use of semiempirical corrections to oxygen in the gas phase. Although such corrections are tacit in the model, they should not be overlooked. In this article, we calculate the errors in the total energy of oxygen for commonly used exchange-correlation functionals, PW91, RPBE, PBE, and BEEF-vdW, to show that, for all functionals tested, the error is at least 0.3 eV. We discuss the impact this sizeable error in oxygen has on the modelling of the ORR and the OER. The error due to oxygen affects not only the overall equilibrium potential of the reaction, but also the energies of individual mechanistic steps. This illustrates that understanding the reasoning behind the semiempirical corrections for oxygen is important for researching new catalysts which may have different potential limiting steps.

AB - DFT modelling of the oxygen reduction and evolution reactions (ORR and OER) habitually makes use of semiempirical corrections to oxygen in the gas phase. Although such corrections are tacit in the model, they should not be overlooked. In this article, we calculate the errors in the total energy of oxygen for commonly used exchange-correlation functionals, PW91, RPBE, PBE, and BEEF-vdW, to show that, for all functionals tested, the error is at least 0.3 eV. We discuss the impact this sizeable error in oxygen has on the modelling of the ORR and the OER. The error due to oxygen affects not only the overall equilibrium potential of the reaction, but also the energies of individual mechanistic steps. This illustrates that understanding the reasoning behind the semiempirical corrections for oxygen is important for researching new catalysts which may have different potential limiting steps.

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