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A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2

Journal Article · · Surface Science
 [1];  [2]
  1. Univ. of Wisconsin, Madison, WI (United States); Lehigh Univ., Bethlehem, PA (United States); University of Wisconsin-Madison Department of Chemical and Biological Engineering
  2. Univ. of Wisconsin, Madison, WI (United States)
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The binding energy of hydrogen sulfide, ammonia, ethane, ethylene, butadiene, benzene, toluene, pyridine, pyrrole, and thiophene on the basal plane of the semi-conducting 2H-molybdenum sulfide (MoS2) was calculated with the following flavors of Density Functional Theory (DFT): GGA-PW91, PBE-D3, vdW-DF, optPBE, optB86b, optB88, vdW-TS, and BEEF-vdW. The GGA-PW91 binding energies are negligible (<0.07 eV in magnitude) in all cases. The predictions with vdW-DF and PBE-D3 are the closest (error <0.05 eV) to the isosteric heats of adsorption calculated from reported temperature programmed desorption data for thiophene and butadiene. For all dispersion flavors examined here, the magnitude of the dispersion contribution to the binding energy increases linearly with the number of heavy atoms in the adsorbate, with each atom contributing 0.05 eV (BEEF-vdW) – 0.09 eV (optB88-vdW). Further, this implies that the calculated adsorption constants of molecules larger than acridine (i.e., comprising > 14 non-heavy atoms) can vary by more than four orders of magnitude at industrial conditions depending on the chosen method of dispersion correction. Further, dispersion effects fall off rapidly (>0.03 eV/ non-hydrogen atom/Å) as the adsorbate-surface distance increases.
Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Contributing Organization:
Argonne National Laboratory (ANL). Center for Nanoscale Materials (CNM); Lawrence Berkeley National Laboratory (LBNL). National Energy Research Scientific Computing Center (NERSC); UW Center For High Throughput Computing (CHTC)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; FG02-05ER15731
OSTI ID:
2007819
Journal Information:
Surface Science, Journal Name: Surface Science Vol. 729; ISSN 0039-6028
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY