Title: DFT-Based Method for More Accurate Adsorption Energies: An Adaptive Sum of Energies from RPBE and vdW Density Functionals

Abstract

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) density functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate thanmore » those of any current standard DFT functional alone.« less

Authors:

Hensley, Alyssa J. R. ^[1]; Ghale, Kushal ^[2]; Rieg, Carolin ^[1]; Dang, Thanh ^[2]; Anderst, Emily ^[1]; Studt, Felix ^[3]; Campbell, Charles T.  ^[4];

• Search DOE PAGES for author "Campbell, Charles T."
• Search DOE PAGES for ORCID "0000-0002-5024-8210"

McEwen, Jean-Sabin  ^[5];

• Search DOE PAGES for author "McEwen, Jean-Sabin"
• Search DOE PAGES for ORCID "0000-0003-0931-4869"

Xu, Ye  ^[2]

• Search DOE PAGES for author "Xu, Ye"
• Search DOE PAGES for ORCID "0000-0002-6406-7832"

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+ Show Author Affiliations

1. Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States
2. Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803, United States
3. Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Karlsruhe 76131, Germany
4. Department of Chemistry and Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, United States
5. Gene & Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, Washington 99164, United States, Department of Physics and Astronomy and Department of Chemistry, Washington State University, Pullman, Washington 99164, United States

Publication Date:

Mon Feb 27 00:00:00 EST 2017

Research Org.:

Washington State Univ., Pullman, WA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1344948

Alternate Identifier(s):

OSTI ID: 1346411

Grant/Contract Number:  

SC0014560

Resource Type:

Published Article

Journal Name:

Journal of Physical Chemistry. C

Additional Journal Information:

Journal Name: Journal of Physical Chemistry. C Journal Volume: 121 Journal Issue: 9; Journal ID: ISSN 1932-7447

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY