Modeling the Oxygen Evolution Reaction on Metal Oxides

The Infuence of Unrestricted DFT Calculations

Rik V Mom, Jun Cheng, Marc TM Koper, Michiel Sprik

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

Due to the contraints imposed on the optimization of oxygen evolution reaction (OER) catalysts, the correlations between adsorption energies of OER intermediates have received considerable interest. Computation has made important contributions uncovering and elucidating these correlations. The calculations have predominantly been of the spin-restricted type. Using both the restricted and unrestricted formalism, we have performed a DFT–PBE study of the key OER intermediates on 10 nonmagnetic metal oxide surfaces. We show that, depending on the binding energy, unrestricted DFT calculations may yield considerably higher binding energies than restricted DFT calculations. At low binding energies, spin quenching of the adsorbates is inefficient, leading to a strong open shell character that is not well described by restricted DFT. At high binding energies, spin quenching is complete, so that the unrestricted DFT binding energy equals the restricted DFT binding energy. We conclude therefore that although strong binding systems can be properly described by restricted DFT, unrestricted DFT is a necessity for weak binding systems, to which photocatalysts typically belong. The use of unrestricted DFT has little effect on the shape of volcano plots when ΔGO – ΔGOH is chosen as a descriptor. The location of the data points on the plot does show a considerable shift for weak binding substrates.
Original languageEnglish
Pages (from-to)4095-4102
Number of pages8
JournalThe Journal of Physical Chemistry C
Volume118
Issue number8
Early online date3 Feb 2014
DOIs
Publication statusPublished - 27 Feb 2014

Fingerprint

Discrete Fourier transforms
Oxides
metal oxides
binding energy
Binding energy
Metals
Oxygen
oxygen
reaction intermediates
Reaction intermediates
plots
quenching
Quenching
volcanoes
Volcanoes
Adsorbates
Photocatalysts
formalism
catalysts
optimization

Cite this

Modeling the Oxygen Evolution Reaction on Metal Oxides : The Infuence of Unrestricted DFT Calculations. / Mom, Rik V; Cheng, Jun; Koper, Marc TM; Sprik, Michiel.

In: The Journal of Physical Chemistry C, Vol. 118, No. 8, 27.02.2014, p. 4095-4102.

Research output: Contribution to journalArticle

Mom, Rik V ; Cheng, Jun ; Koper, Marc TM ; Sprik, Michiel. / Modeling the Oxygen Evolution Reaction on Metal Oxides : The Infuence of Unrestricted DFT Calculations. In: The Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 8. pp. 4095-4102.
@article{3e53c4c5b5da4ccb90040c37d4eabae3,
title = "Modeling the Oxygen Evolution Reaction on Metal Oxides: The Infuence of Unrestricted DFT Calculations",
abstract = "Due to the contraints imposed on the optimization of oxygen evolution reaction (OER) catalysts, the correlations between adsorption energies of OER intermediates have received considerable interest. Computation has made important contributions uncovering and elucidating these correlations. The calculations have predominantly been of the spin-restricted type. Using both the restricted and unrestricted formalism, we have performed a DFT–PBE study of the key OER intermediates on 10 nonmagnetic metal oxide surfaces. We show that, depending on the binding energy, unrestricted DFT calculations may yield considerably higher binding energies than restricted DFT calculations. At low binding energies, spin quenching of the adsorbates is inefficient, leading to a strong open shell character that is not well described by restricted DFT. At high binding energies, spin quenching is complete, so that the unrestricted DFT binding energy equals the restricted DFT binding energy. We conclude therefore that although strong binding systems can be properly described by restricted DFT, unrestricted DFT is a necessity for weak binding systems, to which photocatalysts typically belong. The use of unrestricted DFT has little effect on the shape of volcano plots when ΔGO – ΔGOH is chosen as a descriptor. The location of the data points on the plot does show a considerable shift for weak binding substrates.",
author = "Mom, {Rik V} and Jun Cheng and Koper, {Marc TM} and Michiel Sprik",
year = "2014",
month = "2",
day = "27",
doi = "10.1021/jp409373c",
language = "English",
volume = "118",
pages = "4095--4102",
journal = "The Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "8",

}

TY - JOUR

T1 - Modeling the Oxygen Evolution Reaction on Metal Oxides

T2 - The Infuence of Unrestricted DFT Calculations

AU - Mom, Rik V

AU - Cheng, Jun

AU - Koper, Marc TM

AU - Sprik, Michiel

PY - 2014/2/27

Y1 - 2014/2/27

N2 - Due to the contraints imposed on the optimization of oxygen evolution reaction (OER) catalysts, the correlations between adsorption energies of OER intermediates have received considerable interest. Computation has made important contributions uncovering and elucidating these correlations. The calculations have predominantly been of the spin-restricted type. Using both the restricted and unrestricted formalism, we have performed a DFT–PBE study of the key OER intermediates on 10 nonmagnetic metal oxide surfaces. We show that, depending on the binding energy, unrestricted DFT calculations may yield considerably higher binding energies than restricted DFT calculations. At low binding energies, spin quenching of the adsorbates is inefficient, leading to a strong open shell character that is not well described by restricted DFT. At high binding energies, spin quenching is complete, so that the unrestricted DFT binding energy equals the restricted DFT binding energy. We conclude therefore that although strong binding systems can be properly described by restricted DFT, unrestricted DFT is a necessity for weak binding systems, to which photocatalysts typically belong. The use of unrestricted DFT has little effect on the shape of volcano plots when ΔGO – ΔGOH is chosen as a descriptor. The location of the data points on the plot does show a considerable shift for weak binding substrates.

AB - Due to the contraints imposed on the optimization of oxygen evolution reaction (OER) catalysts, the correlations between adsorption energies of OER intermediates have received considerable interest. Computation has made important contributions uncovering and elucidating these correlations. The calculations have predominantly been of the spin-restricted type. Using both the restricted and unrestricted formalism, we have performed a DFT–PBE study of the key OER intermediates on 10 nonmagnetic metal oxide surfaces. We show that, depending on the binding energy, unrestricted DFT calculations may yield considerably higher binding energies than restricted DFT calculations. At low binding energies, spin quenching of the adsorbates is inefficient, leading to a strong open shell character that is not well described by restricted DFT. At high binding energies, spin quenching is complete, so that the unrestricted DFT binding energy equals the restricted DFT binding energy. We conclude therefore that although strong binding systems can be properly described by restricted DFT, unrestricted DFT is a necessity for weak binding systems, to which photocatalysts typically belong. The use of unrestricted DFT has little effect on the shape of volcano plots when ΔGO – ΔGOH is chosen as a descriptor. The location of the data points on the plot does show a considerable shift for weak binding substrates.

U2 - 10.1021/jp409373c

DO - 10.1021/jp409373c

M3 - Article

VL - 118

SP - 4095

EP - 4102

JO - The Journal of Physical Chemistry C

JF - The Journal of Physical Chemistry C

SN - 1932-7447

IS - 8

ER -