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Title: Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces

Abstract

We assess the accuracy of popular nonempirical GGAs (PBE, PBEsol, RPBE) and meta-GGAs (TPSS, revTPSS, and SCAN) for describing chemisorption reactions at metal surfaces. Except for RPBE, all the functionals tend to overbind the adsorbate significantly. We then propose a nonempirical meta-GGA, denoted as RTPSS, that is based on RPBE in the same way that TPSS is based on PBE. The RTPSS functional remedies the overbinding problem and improves the description of chemisorption energies. As an example of an application of RTPSS, we study the adsorption of CO on Cu surfaces (a notably difficult problem for semilocal functionals) and find that RTPSS is the only tested functional that predicts accurate chemisorption energies and the preferred adsorption site of CO. Although RTPSS gives an accurate description of chemisorption, nonlocal correlation may be necessary to describe physisorption if long-range van der Waals interactions are involved (however, this is true for semilocal functionals in general). We suggest that RTPSS can be a useful meta-GGA for studying chemisorption processes and mechanisms of heterogeneous catalysis.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)
OSTI Identifier:
1477305
Grant/Contract Number:  
[AC02-05CH11231]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
[ Journal Volume: 14; Journal Issue: 6]; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces. United States: N. p., 2018. Web. doi:10.1021/acs.jctc.8b00288.
Garza, Alejandro J., Bell, Alexis T., & Head-Gordon, Martin. Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces. United States. doi:10.1021/acs.jctc.8b00288.
Garza, Alejandro J., Bell, Alexis T., and Head-Gordon, Martin. Thu . "Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces". United States. doi:10.1021/acs.jctc.8b00288. https://www.osti.gov/servlets/purl/1477305.
@article{osti_1477305,
title = {Nonempirical Meta-Generalized Gradient Approximations for Modeling Chemisorption at Metal Surfaces},
author = {Garza, Alejandro J. and Bell, Alexis T. and Head-Gordon, Martin},
abstractNote = {We assess the accuracy of popular nonempirical GGAs (PBE, PBEsol, RPBE) and meta-GGAs (TPSS, revTPSS, and SCAN) for describing chemisorption reactions at metal surfaces. Except for RPBE, all the functionals tend to overbind the adsorbate significantly. We then propose a nonempirical meta-GGA, denoted as RTPSS, that is based on RPBE in the same way that TPSS is based on PBE. The RTPSS functional remedies the overbinding problem and improves the description of chemisorption energies. As an example of an application of RTPSS, we study the adsorption of CO on Cu surfaces (a notably difficult problem for semilocal functionals) and find that RTPSS is the only tested functional that predicts accurate chemisorption energies and the preferred adsorption site of CO. Although RTPSS gives an accurate description of chemisorption, nonlocal correlation may be necessary to describe physisorption if long-range van der Waals interactions are involved (however, this is true for semilocal functionals in general). We suggest that RTPSS can be a useful meta-GGA for studying chemisorption processes and mechanisms of heterogeneous catalysis.},
doi = {10.1021/acs.jctc.8b00288},
journal = {Journal of Chemical Theory and Computation},
number = [6],
volume = [14],
place = {United States},
year = {2018},
month = {5}
}

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