A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2
Abstract
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.
- Authors:
-
[1];
- Univ. of Wisconsin, Madison, WI (United States); Lehigh Univ., Bethlehem, PA (United States)
- Univ. of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- Contributing Org.:
- 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)
- OSTI Identifier:
- 2007819
- Grant/Contract Number:
- FG02-05ER15731; AC02–06CH11357; AC02–05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 729; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rangarajan, Srinivas, and Mavrikakis, Manos. A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2. United States: N. p., 2022.
Web. doi:10.1016/j.susc.2022.122226.
Rangarajan, Srinivas, & Mavrikakis, Manos. A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2. United States. https://doi.org/10.1016/j.susc.2022.122226
Rangarajan, Srinivas, and Mavrikakis, Manos. Wed .
"A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2". United States. https://doi.org/10.1016/j.susc.2022.122226. https://www.osti.gov/servlets/purl/2007819.
@article{osti_2007819,
title = {A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS2},
author = {Rangarajan, Srinivas and Mavrikakis, Manos},
abstractNote = {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.},
doi = {10.1016/j.susc.2022.122226},
journal = {Surface Science},
number = ,
volume = 729,
place = {United States},
year = {Wed Nov 23 00:00:00 EST 2022},
month = {Wed Nov 23 00:00:00 EST 2022}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics
journal, January 2012
- Zaman, Sharif; Smith, Kevin J.
- Catalysis Reviews, Vol. 54, Issue 1
Many-body dispersion effects in the binding of adsorbates on metal surfaces
journal, September 2015
- Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre
- The Journal of Chemical Physics, Vol. 143, Issue 10
Enhanced Hydrogen Evolution Catalysis from Chemically Exfoliated Metallic MoS 2 Nanosheets
journal, May 2013
- Lukowski, Mark A.; Daniel, Andrew S.; Meng, Fei
- Journal of the American Chemical Society, Vol. 135, Issue 28
Density-Functional Theory with Screened van der Waals Interactions for the Modeling of Hybrid Inorganic-Organic Systems
journal, April 2012
- Ruiz, Victor G.; Liu, Wei; Zojer, Egbert
- Physical Review Letters, Vol. 108, Issue 14
An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel
journal, November 2003
- Song, Chunshan
- Catalysis Today, Vol. 86, Issue 1-4
Present progress in the development of low friction coatings
journal, March 1996
- Hirvonen, J. -P.; Koskinen, J.; Jervis, J. R.
- Surface and Coatings Technology, Vol. 80, Issue 1-2
Van der Waals density functionals applied to solids
journal, May 2011
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Physical Review B, Vol. 83, Issue 19
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Adsorption of nitrogen- and sulfur-containing compounds on NiMoS for hydrotreating reactions: A DFT and vdW-corrected study
journal, September 2015
- Rangarajan, Srinivas; Mavrikakis, Manos
- AIChE Journal, Vol. 61, Issue 12
Optimization of Effective Atom Centered Potentials for London Dispersion Forces in Density Functional Theory
journal, October 2004
- von Lilienfeld, O. Anatole; Tavernelli, Ivano; Rothlisberger, Ursula
- Physical Review Letters, Vol. 93, Issue 15
Emerging Photoluminescence in Monolayer MoS2
journal, April 2010
- Splendiani, Andrea; Sun, Liang; Zhang, Yuanbo
- Nano Letters, Vol. 10, Issue 4, p. 1271-1275
DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts
journal, April 2016
- Rangarajan, Srinivas; Mavrikakis, Manos
- ACS Catalysis, Vol. 6, Issue 5
Gas adsorption on MoS2 monolayer from first-principles calculations
journal, March 2014
- Zhao, Shijun; Xue, Jianming; Kang, Wei
- Chemical Physics Letters, Vol. 595-596
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Molecular tests of the random phase approximation to the exchange-correlation energy functional
journal, October 2001
- Furche, Filipp
- Physical Review B, Vol. 64, Issue 19
Chemical accuracy for the van der Waals density functional
journal, December 2009
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Journal of Physics: Condensed Matter, Vol. 22, Issue 2
A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions
journal, January 2011
- Goerigk, Lars; Grimme, Stefan
- Physical Chemistry Chemical Physics, Vol. 13, Issue 14
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
Improved Description of the Structure of Molecular and Layered Crystals: Ab Initio DFT Calculations with van der Waals Corrections
journal, November 2010
- Bučko, Tomáš; Hafner, Jürgen; Lebègue, Sébastien
- The Journal of Physical Chemistry A, Vol. 114, Issue 43
Are we van der Waals ready?
journal, October 2012
- Björkman, T.; Gulans, A.; Krasheninnikov, A. V.
- Journal of Physics: Condensed Matter, Vol. 24, Issue 42
Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 25, Issue 12
Atomically Thin A New Direct-Gap Semiconductor
journal, September 2010
- Mak, Kin Fai; Lee, Changgu; Hone, James
- Physical Review Letters, Vol. 105, Issue 13, Article No.136805
Fabrication of Single- and Multilayer MoS2 Film-Based Field-Effect Transistors for Sensing NO at Room Temperature
journal, October 2011
- Li, Hai; Yin, Zongyou; He, Qiyuan
- Small, Vol. 8, Issue 1
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012
- Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas
- Physical Review B, Vol. 85, Issue 23
van der Waals forces in density functional theory: a review of the vdW-DF method
journal, May 2015
- Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho
- Reports on Progress in Physics, Vol. 78, Issue 6
Density functional calculations of molecular bond energies
journal, April 1986
- Becke, A. D.
- The Journal of Chemical Physics, Vol. 84, Issue 8
Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces
journal, February 2014
- Carrasco, Javier; Liu, Wei; Michaelides, Angelos
- The Journal of Chemical Physics, Vol. 140, Issue 8
van der Waals Bonding in Layered Compounds from Advanced Density-Functional First-Principles Calculations
journal, June 2012
- Björkman, T.; Gulans, A.; Krasheninnikov, A. V.
- Physical Review Letters, Vol. 108, Issue 23
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Fabrication of Flexible MoS2 Thin-Film Transistor Arrays for Practical Gas-Sensing Applications
journal, July 2012
- He, Qiyuan; Zeng, Zhiyuan; Yin, Zongyou
- Small, Vol. 8, Issue 19, p. 2994-2999
Active sites speciation of supported CoMoS phase probed by NO molecule: A combined IR and DFT study
journal, May 2018
- Caron, Fabien; Rivallan, Mickaël; Humbert, Séverine
- Journal of Catalysis, Vol. 361
Costless Derivation of Dispersion Coefficients for Metal Surfaces
journal, October 2014
- Almora-Barrios, Neyvis; Carchini, Giuliano; Błoński, Piotr
- Journal of Chemical Theory and Computation, Vol. 10, Issue 11
Inhibition effects observed between dibenzothiophene and carbazole during the hydrotreating process
journal, July 2004
- Laredo, G.
- Applied Catalysis A: General, Vol. 265, Issue 2
Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS 2 surface via single-atom metal doping
journal, January 2015
- Deng, Jiao; Li, Haobo; Xiao, Jianping
- Energy & Environmental Science, Vol. 8, Issue 5
Advanced solid lubricant coatings for high vacuum environments
journal, March 1996
- Donnet, C.
- Surface and Coatings Technology, Vol. 80, Issue 1-2
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
The adsorption and binding of thiophene, butene and H2S on the basal plane of MoS2 single crystals
journal, July 1982
- Salmeron, M.; Somorjai, G. A.; Wold, A.
- Chemical Physics Letters, Vol. 90, Issue 2
Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis
journal, October 2012
- Kibsgaard, Jakob; Chen, Zhebo; Reinecke, Benjamin N.
- Nature Materials, Vol. 11, Issue 11, p. 963-969
Free-energy profiles along reduction pathways of MoS2 M-edge and S-edge by dihydrogen: A first-principles study
journal, June 2011
- Prodhomme, Pierre-Yves; Raybaud, Pascal; Toulhoat, Hervé
- Journal of Catalysis, Vol. 280, Issue 2
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene
journal, August 2020
- Salazar, Norberto; Rangarajan, Srinivas; Rodríguez-Fernández, Jonathan
- Nature Communications, Vol. 11, Issue 1
Accurate Bulk Properties from Approximate Many-Body Techniques
journal, July 2009
- Harl, Judith; Kresse, Georg
- Physical Review Letters, Vol. 103, Issue 5
MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction
journal, March 2017
- Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung
- Nature Chemistry, Vol. 9, Issue 8
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
A benchmark for non-covalent interactions in solids
journal, August 2012
- Otero-de-la-Roza, A.; Johnson, Erin R.
- The Journal of Chemical Physics, Vol. 137, Issue 5
Seamless and Accurate Modeling of Organic Molecular Materials
journal, March 2013
- Reilly, Anthony M.; Tkatchenko, Alexandre
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
A study of the lubricating mechanism of molybdenum disulfide
journal, March 1972
- Holinski, R.; Gänsheimer, J.
- Wear, Vol. 19, Issue 3
Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
journal, September 2012
- Klimeš, Jiří; Michaelides, Angelos
- The Journal of Chemical Physics, Vol. 137, Issue 12
Accurate and Efficient Method for Many-Body van der Waals Interactions
journal, June 2012
- Tkatchenko, Alexandre; DiStasio, Robert A.; Car, Roberto
- Physical Review Letters, Vol. 108, Issue 23
Atomic-scale insight into structure and morphology changes of MoS2 nanoclusters in hydrotreating catalysts
journal, January 2004
- Lauritsen, J. V.; Bollinger, M. V.; Lægsgaard, E.
- Journal of Catalysis, Vol. 221, Issue 2, p. 510-522
Layer-Dependent Electrocatalysis of MoS 2 for Hydrogen Evolution
journal, January 2014
- Yu, Yifei; Huang, Sheng-Yang; Li, Yanpeng
- Nano Letters, Vol. 14, Issue 2
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992
- Perdew, John P.; Chevary, J. A.; Vosko, S. H.
- Physical Review B, Vol. 46, Issue 11
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
Sulfur vacancy-rich MoS2 as a catalyst for the hydrogenation of CO2 to methanol
journal, March 2021
- Hu, Jingting; Yu, Liang; Deng, Jiao
- Nature Catalysis, Vol. 4, Issue 3
Density functional theory with London dispersion corrections: Density functional theory with London dispersion corrections
journal, March 2011
- Grimme, Stefan
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992
- Neugebauer, Jörg; Scheffler, Matthias
- Physical Review B, Vol. 46, Issue 24
Ultrasensitive photodetectors based on monolayer MoS2
journal, June 2013
- Lopez-Sanchez, Oriol; Lembke, Dominik; Kayci, Metin
- Nature Nanotechnology, Vol. 8, Issue 7
On the Preferred Active Sites of Promoted MoS 2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition
journal, December 2016
- Rangarajan, Srinivas; Mavrikakis, Manos
- ACS Catalysis, Vol. 7, Issue 1
Tkatchenko-Scheffler van der Waals correction method with and without self-consistent screening applied to solids
journal, February 2013
- Bučko, Tomáš; Lebègue, S.; Hafner, Jürgen
- Physical Review B, Vol. 87, Issue 6
Inhibition of the Hydrogenation and Hydrodesulfurization Reactions by Nitrogen Compounds over NiMo/Al2O3
journal, April 2008
- Beltramone, A. R.; Crossley, S.; Resasco, D. E.
- Catalysis Letters, Vol. 123, Issue 3-4
Stacking effects on the electronic and optical properties of bilayer transition metal dichalcogenides , , , and
journal, February 2014
- He, Jiangang; Hummer, Kerstin; Franchini, Cesare
- Physical Review B, Vol. 89, Issue 7
Modeling Adsorption and Reactions of Organic Molecules at Metal Surfaces
journal, June 2014
- Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias
- Accounts of Chemical Research, Vol. 47, Issue 11
Density functional study of the adsorption and van der Waals binding of aromatic and conjugated compounds on the basal plane of MoS2
journal, March 2009
- Moses, Poul Georg; Mortensen, Jens J.; Lundqvist, Bengt I.
- The Journal of Chemical Physics, Vol. 130, Issue 10
Sensing Behavior of Atomically Thin-Layered MoS 2 Transistors
journal, May 2013
- Late, Dattatray J.; Huang, Yi-Kai; Liu, Bin
- ACS Nano, Vol. 7, Issue 6
Single-layer MoS2 transistors
journal, January 2011
- Radisavljevic, B.; Radenovic, A.; Brivio, J.
- Nature Nanotechnology, Vol. 6, Issue 3, p. 147-150
Activating Inert Basal Planes of MoS 2 for Hydrogen Evolution Reaction through the Formation of Different Intrinsic Defects
journal, June 2016
- Ouyang, Yixin; Ling, Chongyi; Chen, Qian
- Chemistry of Materials, Vol. 28, Issue 12
Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production
journal, July 2010
- Stanislaus, Antony; Marafi, Abdulazeem; Rana, Mohan S.
- Catalysis Today, Vol. 153, Issue 1-2