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Title: Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-043, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388270
DOE Contract Number:
SC0012702
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Theory and Computation; Journal Volume: 13; Journal Issue: 2; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), materials and chemistry by design, synthesis (novel materials)

Citation Formats

Duanmu, Kaining, and Truhlar, Donald G. Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.6b01156.
Duanmu, Kaining, & Truhlar, Donald G. Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces. United States. doi:10.1021/acs.jctc.6b01156.
Duanmu, Kaining, and Truhlar, Donald G. Tue . "Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces". United States. doi:10.1021/acs.jctc.6b01156.
@article{osti_1388270,
title = {Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces},
author = {Duanmu, Kaining and Truhlar, Donald G.},
abstractNote = {},
doi = {10.1021/acs.jctc.6b01156},
journal = {Journal of Chemical Theory and Computation},
number = 2,
volume = 13,
place = {United States},
year = {Tue Jan 03 00:00:00 EST 2017},
month = {Tue Jan 03 00:00:00 EST 2017}
}
  • Cited by 58
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  • 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) densitymore » 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 than those of any current standard DFT functional alone.« less
    Cited by 3
  • 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) densitymore » 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 than those of any current standard DFT functional alone.« less