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Title: DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

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:
 [1] ;  [2] ;  [1] ;  [2] ;  [1] ;  [3] ; ORCiD logo [4] ; ORCiD logo [1] ; ORCiD logo [2]
  1. Washington State Univ., Pullman, WA (United States)
  2. Louisiana State Univ., Baton Rouge, LA (United States)
  3. Karlsruhe Institute of Technology, Karlsruhe (Germany)
  4. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Grant/Contract Number:
SC0014560
Type:
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 9; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1344948
Alternate Identifier(s):
OSTI ID: 1346411