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

Abstract

Semi-local 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 semi-local functionals require an additive non-local 1 arXiv:1906.01091v2 [cond-mat.mtrl-sci] 5 Jun 2019 correction such as the revised Vydrov-Van Voorhis 2010 (rVV10) to capture the longrange part. This work reports adsorption energies and the corresponding geometry of the aromatic thiophene (C 4 H 4 S) 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.

Effects of van der Waals Dispersion Interactions in Density Functional Studies of Adsorption, Catalysis, and Tribology on Metals

“…Further, Berland et al developed hybrid vdW-DF methods (e.g., hybrid-vdW-DF-cx and hydrid-vdW-DF2) by combining the Fock exchange with the vdW-DF-cx or vdW-DF2 correlation functional. , This was implemented in Quantum espresso and FHi-ABINIT codes and demonstrated high accuracy for studies of small halogenated molecules. Additionally, Vydrov and Van Voorhis derived some simple nonlocal correlation functionals, e.g., VV09, , VV10, and rVV10, which perform well through appropriate combinations of HF, GGA, and meta-GGA (mGGA) functionals. − For instance, the rVV10-corrected SCAN meta-GGA method (SCAN+rVV10) can accurately predict the adsorption energies and adsorption geometries of benzene on metal surfaces, better than the results obtained with vdW-DF, PBE-vdW surf , and DFT+D methods . The applicability and reliability of the DFT-D n corrections are limited by the accuracy of the system-dependent dispersion coefficients and damping functions, whereas the accuracy of the vdW-DF methods is closely related to the choice of exchange functionals.…”

STM Investigation of the Y[C6S-Pc]2 and Y[C4O-Pc]2Complex at the Solution–Solid Interface: Substrate Effects, Submolecular Resolution, and Vacancies

“…In direct conflict with early theoretical predictions, Dishner et al were able to observe STM images of self-assembly of thiophene on Au(111) by immersion in an ethanolic solution . Following Dishner’s work, several authors investigated the thiophene–Au(111) system and determined that, at low coverages, the molecule adsorbed reversibly (no S–C bond cleavage) and that the thiophene lay nearly parallel to the gold surface. − Temperature-programmed desorption measurements indicate that the reversible desorption energy is near 0.65 eV. , More recent density functional treatments of the thiophene–Au(111) system give reasonable agreement with experiment. , A small but informative body of literature also exists for the dialkylsulfides adsorbed on gold. These studies also indicate that the dialkylsulfides adsorb reversibly without cleavage of the S–C bonds and that the alkane chains tend to lay parallel to the surface at low surface coverage. ,, Interestingly, diethylsulfide is reported to have a desorption energy larger than that for thiophene .…”

“…55,57 More recent density functional treatments of the thiophene− Au(111) system give reasonable agreement with experiment. 43,58 A small but informative body of literature also exists for the dialkylsulfides adsorbed on gold. These studies also indicate that the dialkylsulfides adsorb reversibly without cleavage of the S−C bonds and that the alkane chains tend to lay parallel to the surface at low surface coverage.…”

Exploring and enhancing the accuracy of interior-scaled Perdew–Zunger self-interaction correction

“…LSIC and LSIC+ are applied to LSDA, but they produce results close to SCAN results and sometimes even better. Because of the predictive power and success of SCAN 17,[40][41][42][43][44][45] , the LSDA-LSIC and LSDA-LSIC+ results are primarily compared with SCAN, SCAN-SIC 46 , and SCAN-sdSIC results.…”