Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?
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, (...
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2019
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| Online Access: | https://hdl.handle.net/1721.1/123204 |
| _version_ | 1826207008620019712 |
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| author | Zhao, Qing Kulik, Heather Janine |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Zhao, Qing Kulik, Heather Janine |
| author_sort | Zhao, Qing |
| collection | MIT |
| description | 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- A nd 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. |
| first_indexed | 2024-09-23T13:42:03Z |
| format | Article |
| id | mit-1721.1/123204 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T13:42:03Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1232042022-10-01T16:39:07Z Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? Zhao, Qing Kulik, Heather Janine Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Mechanical Engineering General Materials Science 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- A nd 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. 2019-12-10T20:16:02Z 2019-12-10T20:16:02Z 2019-08 2019-06 2019-10-10T15:59:27Z Article http://purl.org/eprint/type/JournalArticle 1948-7185 1948-7185 https://hdl.handle.net/1721.1/123204 Zhao, Qing and Heather J. Kulik. "Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry?." Journal of Physical Chemistry Letters 10, 17 (August 2019): 5090-5098 © 2019 American Chemical Society en http://dx.doi.org/10.1021/acs.jpclett.9b01650 Journal of Physical Chemistry Letters Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | General Materials Science Zhao, Qing Kulik, Heather Janine Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title | Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title_full | Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title_fullStr | Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title_full_unstemmed | Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title_short | Stable Surfaces That Bind Too Tightly: Can Range-Separated Hybrids or DFT+U Improve Paradoxical Descriptions of Surface Chemistry? |
| title_sort | stable surfaces that bind too tightly can range separated hybrids or dft u improve paradoxical descriptions of surface chemistry |
| topic | General Materials Science |
| url | https://hdl.handle.net/1721.1/123204 |
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