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Title: Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces

Abstract

Semilocal density functional approximations are widely used. None of them can capture the long-range van der Waals (vdW) attraction between separated subsystems, but they differ remarkably in the extent to which they capture intermediate-range vdW effects responsible for equilibrium bonds between neighboring small closed-shell subsystems. The local density approximation (LDA) often overestimates this effect, while the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) underestimates it. The strongly constrained and appropriately normed (SCAN) meta-GGA often estimates it well. All of these semilocal functionals require an additive nonlocal correction such as the revised Vydrov-Van Voorhis 2010 (rVV10) to capture the long-range part. This work reports adsorption energies and the corresponding geometry of aromatic thiophene (C4H4S) bound to transition-metal surfaces. The adsorption process requires a genuine interplay of covalent and weak binding and requires a simultaneously accurate description of surface and adsorption energies with the correct prediction of the adsorption site. All these quantities must come from well-balanced short- and long-range correlation effects for a universally applicable method for weak interactions with chemical accuracy. Here, our methods indicate that the correct interplay is not present in any combination of recent meta-GGA's and rVV10. The simple short-range damping of the vdW correction scheme that ismore » practically successful in the combination of GGA's and vdW approximations is less transferable in SCAN+rVV10 or in the revised version, revSCAN+rVV10. In addition, we present accurate random-phase-approximation-quality adsorption energies from a model based on the one of Zaremba and Kohn.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
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  1. Temple Univ., Philadelphia, PA (United States)
  2. Budapest Univ. of Technology and Economics, Budapest (Hungary)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1608626
Alternate Identifier(s):
OSTI ID: 1602357
Grant/Contract Number:  
SC0012575; SC0018194
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 4; Journal Issue: 2; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Adhikari, Santosh, Tang, Hong, Neupane, Bimal, Ruzsinszky, Adrienn, and Csonka, Gábor I. Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces. United States: N. p., 2020. Web. doi:10.1103/PhysRevMaterials.4.025005.
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Adhikari, Santosh, Tang, Hong, Neupane, Bimal, Ruzsinszky, Adrienn, & Csonka, Gábor I. Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces. United States. https://doi.org/10.1103/PhysRevMaterials.4.025005
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Adhikari, Santosh, Tang, Hong, Neupane, Bimal, Ruzsinszky, Adrienn, and Csonka, Gábor I. Thu . "Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces". United States. https://doi.org/10.1103/PhysRevMaterials.4.025005. https://www.osti.gov/servlets/purl/1608626.
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@article{osti_1608626,
title = {Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces},
author = {Adhikari, Santosh and Tang, Hong and Neupane, Bimal and Ruzsinszky, Adrienn and Csonka, Gábor I.},
abstractNote = {Semilocal density functional approximations are widely used. None of them can capture the long-range van der Waals (vdW) attraction between separated subsystems, but they differ remarkably in the extent to which they capture intermediate-range vdW effects responsible for equilibrium bonds between neighboring small closed-shell subsystems. The local density approximation (LDA) often overestimates this effect, while the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) underestimates it. The strongly constrained and appropriately normed (SCAN) meta-GGA often estimates it well. All of these semilocal functionals require an additive nonlocal correction such as the revised Vydrov-Van Voorhis 2010 (rVV10) to capture the long-range part. This work reports adsorption energies and the corresponding geometry of aromatic thiophene (C4H4S) bound to transition-metal surfaces. The adsorption process requires a genuine interplay of covalent and weak binding and requires a simultaneously accurate description of surface and adsorption energies with the correct prediction of the adsorption site. All these quantities must come from well-balanced short- and long-range correlation effects for a universally applicable method for weak interactions with chemical accuracy. Here, our methods indicate that the correct interplay is not present in any combination of recent meta-GGA's and rVV10. The simple short-range damping of the vdW correction scheme that is practically successful in the combination of GGA's and vdW approximations is less transferable in SCAN+rVV10 or in the revised version, revSCAN+rVV10. In addition, we present accurate random-phase-approximation-quality adsorption energies from a model based on the one of Zaremba and Kohn.},
doi = {10.1103/PhysRevMaterials.4.025005},
journal = {Physical Review Materials},
number = 2,
volume = 4,
place = {United States},
year = {Thu Feb 27 00:00:00 EST 2020},
month = {Thu Feb 27 00:00:00 EST 2020}
}
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https://doi.org/10.1103/PhysRevMaterials.4.025005
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