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Title: Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?

Abstract

Approximate, semilocal density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical model of catalytic surfaces that both overbind adsorbates yet are also too stable. We investigate the effect of two widely applied approaches for delocalization error correction, (i) affordable DFT+U (i.e., semilocal DFT augmented with a Hubbard U) and (ii) hybrid functionals with an admixture of Hartree–Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water-splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti and V) and decreases adsorbate energies only in later transition metals (e.g., Ir and Pt). Both global and local hybrids destabilize surfaces and reduce adsorbate binding across the periodic table, in agreement with higher-level reference calculations. Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not. We recommend local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semilocal DFT.

Authors:
 [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1560126
Grant/Contract Number:  
SC0018096
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 10; Journal Issue: 17; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Qing, and Kulik, Heather J. Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.9b01650.
Zhao, Qing, & Kulik, Heather J. Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?. United States. doi:10.1021/acs.jpclett.9b01650.
Zhao, Qing, and Kulik, Heather J. Wed . "Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?". United States. doi:10.1021/acs.jpclett.9b01650. https://www.osti.gov/servlets/purl/1560126.
@article{osti_1560126,
title = {Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?},
author = {Zhao, Qing and Kulik, Heather J.},
abstractNote = {Approximate, semilocal density functional theory (DFT) suffers from delocalization error that can lead to a paradoxical model of catalytic surfaces that both overbind adsorbates yet are also too stable. We investigate the effect of two widely applied approaches for delocalization error correction, (i) affordable DFT+U (i.e., semilocal DFT augmented with a Hubbard U) and (ii) hybrid functionals with an admixture of Hartree–Fock (HF) exchange, on surface and adsorbate energies across a range of rutile transition metal oxides widely studied for their promise as water-splitting catalysts. We observe strongly row- and period-dependent trends with DFT+U, which increases surface formation energies only in early transition metals (e.g., Ti and V) and decreases adsorbate energies only in later transition metals (e.g., Ir and Pt). Both global and local hybrids destabilize surfaces and reduce adsorbate binding across the periodic table, in agreement with higher-level reference calculations. Density analysis reveals why hybrid functionals correct both quantities, whereas DFT+U does not. We recommend local, range-separated hybrids for the accurate modeling of catalysis in transition metal oxides at only a modest increase in computational cost over semilocal DFT.},
doi = {10.1021/acs.jpclett.9b01650},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 17,
volume = 10,
place = {United States},
year = {2019},
month = {8}
}

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Figures / Tables:

Figure 1 Figure 1: MO2 structures: (left, side-view) pristine 48-atom surface model for calculating $E$σ and (middle, side-view; right, top-view) O atom adsorption for 0.5 monolayer (ML) coverage used to calculate $ΔE$O. The clear square in the rightmost panel indicates unique atoms in a single unit cell, and representative lattice parameters formore » TiO2 are shown. Atoms are colored as follows: metal atom in blue, MO2 oxygen atom in red, and adsorbate oxygen atom in orange.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.