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

Journal Article · · Physical Review Materials
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]
  1. Temple Univ., Philadelphia, PA (United States)
  2. Budapest Univ. of Technology and Economics, Budapest (Hungary)
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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.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012575; SC0018194
OSTI ID:
1608626
Alternate ID(s):
OSTI ID: 1602357
Journal Information:
Physical Review Materials, Vol. 4, Issue 2; ISSN 2475-9953
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

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