Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A van der Waals Inclusive Density Functional Theory Study of the Nature of Bonding for Thiophene Adsorption on Ni(100) and Cu(100) Surfaces

Abstract

We report the results of the first-principles density functional theory calculations for the adsorption of thiophene (C4H4S) on Cu(100) and Ni(100) surfaces. The adsorption properties on these surfaces are evaluated for several adsorption configurations, and the calculations are performed with the inclusion of van der Waals (vdW) interactions invoking the optimized vdW (optB86b-vdW, optB88-vdW, and optPBE-vdW) as well as revPBE-vdW and rPW86-vdW2 functionals. In agreement with the earlier reports, on both surfaces, the most stable adsorption configurations correspond to the hollow-45 at which the thiophene adsorbs parallel to the surface. For the adsorption on Ni(100), in agreement with the experimental observations, we confirm that thiophene spontaneously ruptures via breaking of a C–S bond when the center of the molecule is placed over a bridge site. On the basis of both the bond distribution and charge transfer analysis, we conclude that the rupturing of thiophene observed at the bridge-45 configuration on Ni(100) may result from large charge transfer from the surface. The analyses of the electronic and geometric structures and charge transfer reveal that the interaction of the thiophene molecule with Ni(100) is much stronger than that of the Cu(100) surface. Upon adsorption of the molecule, for the former surface, wemore » observed much larger charge transfer, non-negligible changes in the positions of the surface atoms, and appreciable electronic structure changes (i.e., in the center and width of the d-band). The adsorption of thiophene on Ni(100) also leads to the decrease in the magnetic moment of the surface Ni atoms particularly those in the vicinity of the adsorbed molecule. All these observations considered, we conclude that the nature of bonding on Ni(100) can be classified as strong chemisorption, while on Cu(100) it can be classified between weak and strong physisorption depending on the vdW functional used.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Central Florida, Orlando, FL (United States). Physics Dept.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1480450
Grant/Contract Number:  
FG02-11ER16243; SC0007045
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 11; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Thiophene; Molecular Adsorption; Charge Transfer; Magnetization; Ni(100) and Cu(100); van der Waals (vdW) Interactions; Density functional theory (DFT)

Citation Formats

Malone, Walter, Yildirim, Handan, Matos, Jeronimo, and Kara, Abdelkader. A van der Waals Inclusive Density Functional Theory Study of the Nature of Bonding for Thiophene Adsorption on Ni(100) and Cu(100) Surfaces. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.6b12064.
Copy to clipboard
Malone, Walter, Yildirim, Handan, Matos, Jeronimo, & Kara, Abdelkader. A van der Waals Inclusive Density Functional Theory Study of the Nature of Bonding for Thiophene Adsorption on Ni(100) and Cu(100) Surfaces. United States. https://doi.org/10.1021/acs.jpcc.6b12064
Copy to clipboard
Malone, Walter, Yildirim, Handan, Matos, Jeronimo, and Kara, Abdelkader. Thu . "A van der Waals Inclusive Density Functional Theory Study of the Nature of Bonding for Thiophene Adsorption on Ni(100) and Cu(100) Surfaces". United States. https://doi.org/10.1021/acs.jpcc.6b12064. https://www.osti.gov/servlets/purl/1480450.
Copy to clipboard
@article{osti_1480450,
title = {A van der Waals Inclusive Density Functional Theory Study of the Nature of Bonding for Thiophene Adsorption on Ni(100) and Cu(100) Surfaces},
author = {Malone, Walter and Yildirim, Handan and Matos, Jeronimo and Kara, Abdelkader},
abstractNote = {We report the results of the first-principles density functional theory calculations for the adsorption of thiophene (C4H4S) on Cu(100) and Ni(100) surfaces. The adsorption properties on these surfaces are evaluated for several adsorption configurations, and the calculations are performed with the inclusion of van der Waals (vdW) interactions invoking the optimized vdW (optB86b-vdW, optB88-vdW, and optPBE-vdW) as well as revPBE-vdW and rPW86-vdW2 functionals. In agreement with the earlier reports, on both surfaces, the most stable adsorption configurations correspond to the hollow-45 at which the thiophene adsorbs parallel to the surface. For the adsorption on Ni(100), in agreement with the experimental observations, we confirm that thiophene spontaneously ruptures via breaking of a C–S bond when the center of the molecule is placed over a bridge site. On the basis of both the bond distribution and charge transfer analysis, we conclude that the rupturing of thiophene observed at the bridge-45 configuration on Ni(100) may result from large charge transfer from the surface. The analyses of the electronic and geometric structures and charge transfer reveal that the interaction of the thiophene molecule with Ni(100) is much stronger than that of the Cu(100) surface. Upon adsorption of the molecule, for the former surface, we observed much larger charge transfer, non-negligible changes in the positions of the surface atoms, and appreciable electronic structure changes (i.e., in the center and width of the d-band). The adsorption of thiophene on Ni(100) also leads to the decrease in the magnetic moment of the surface Ni atoms particularly those in the vicinity of the adsorbed molecule. All these observations considered, we conclude that the nature of bonding on Ni(100) can be classified as strong chemisorption, while on Cu(100) it can be classified between weak and strong physisorption depending on the vdW functional used.},
doi = {10.1021/acs.jpcc.6b12064},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 121,
place = {United States},
year = {Thu Feb 23 00:00:00 EST 2017},
month = {Thu Feb 23 00:00:00 EST 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.6b12064
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Present State of the Art and Future Challenges in the Hydrodesulfurization of Polyaromatic Sulfur Compounds
book, January 1998

Model studies of the desulfurization reactions on metal surfaces and in organometallic complexes
journal, June 1992

  • Wiegand, Benjamin C.; Friend, Cynthia M.
  • Chemical Reviews, Vol. 92, Issue 4
  • DOI: 10.1021/cr00012a001

Multicolor oligothiophene-based light-emitting diodes
journal, March 2001

  • Gigli, G.; Inganäs, O.; Anni, M.
  • Applied Physics Letters, Vol. 78, Issue 11
  • DOI: 10.1063/1.1355991

Beyond the local-density approximation in calculations of ground-state electronic properties
journal, August 1983

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992

van der Waals forces in density functional theory: a review of the vdW-DF method
journal, May 2015

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
  • DOI: 10.1002/jcc.20495

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
  • DOI: 10.1063/1.3382344

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
  • DOI: 10.1088/0953-8984/22/2/022201

Higher-accuracy van der Waals density functional
journal, August 2010

Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009

The role of van der Waals forces in water adsorption on metals
journal, January 2013

  • Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773901

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
  • DOI: 10.1063/1.4754130

Van der Waals Interactions Between Organic Adsorbates and at Organic/Inorganic Interfaces
journal, June 2010

  • Tkatchenko, Alexandre; Romaner, Lorenz; Hofmann, Oliver T.
  • MRS Bulletin, Vol. 35, Issue 6
  • DOI: 10.1557/mrs2010.581

Trends in Adsorption Characteristics of Benzene on Transition Metal Surfaces: Role of Surface Chemistry and van der Waals Interactions
journal, September 2013

  • Yildirim, Handan; Greber, Thomas; Kara, Abdelkader
  • The Journal of Physical Chemistry C, Vol. 117, Issue 40
  • DOI: 10.1021/jp404487z

Insight into the Effect of Long Range Interactions for the Adsorption of Benzene on Transition Metal (110) Surfaces
journal, January 2015

  • Matos, Jeronimo; Yildirim, Handan; Kara, Abdelkader
  • The Journal of Physical Chemistry C, Vol. 119, Issue 4
  • DOI: 10.1021/jp511268s

Effect of van der Waals Interactions on the Adsorption of Olympicene Radical on Cu(111): Characteristics of Weak Physisorption versus Strong Chemisorption
journal, February 2013

  • Yildirim, Handan; Kara, Abdelkader
  • The Journal of Physical Chemistry C, Vol. 117, Issue 6
  • DOI: 10.1021/jp311361e

On the role of long range interactions for the adsorption of sexithiophene on Ag(110) surface
journal, April 2014

  • Matos, Jeronimo; Rojas, Tomas; Yildirim, Handan
  • The Journal of Chemical Physics, Vol. 140, Issue 14
  • DOI: 10.1063/1.4870459

Role of Long-Range Interactions for the Structure and Energetics of Olympicene Radical Adsorbed on Au(111) and Pt(111) Surfaces
journal, November 2015

  • Yildirim, Handan; Matos, Jeronimo; Kara, Abdelkader
  • The Journal of Physical Chemistry C, Vol. 119, Issue 45
  • DOI: 10.1021/acs.jpcc.5b08191

Cyano-Functionalized Triarylamines on Au(111): Competing Intermolecular versus Molecule/Substrate Interactions
journal, November 2013

  • Gottardi, Stefano; Müller, Kathrin; Moreno-López, Juan Carlos
  • Advanced Materials Interfaces, Vol. 1, Issue 1
  • DOI: 10.1002/admi.201300025

Cyano-Functionalized Triarylamines on Coinage Metal Surfaces: Interplay of Intermolecular and Molecule-Substrate Interactions
journal, December 2015

  • Müller , Kathrin; Moreno-López, Juan Carlos; Gottardi, Stefano
  • Chemistry - A European Journal, Vol. 22, Issue 2
  • DOI: 10.1002/chem.201503205

A density-functional model of the dispersion interaction
journal, October 2005

  • Becke, Axel D.; Johnson, Erin R.
  • The Journal of Chemical Physics, Vol. 123, Issue 15
  • DOI: 10.1063/1.2065267

Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007

Nonlocal van der Waals Density Functional Made Simple
journal, August 2009

Investigation of Exchange Energy Density Functional Accuracy for Interacting Molecules
journal, August 2009

  • Murray, Éamonn D.; Lee, Kyuho; Langreth, David C.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct900365q

Molecular tests of the random phase approximation to the exchange-correlation energy functional
journal, October 2001

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
  • DOI: 10.1103/PhysRevLett.77.3865

Structural and electronic properties of adsorbed C4H4S on Cu(100) and Ni(100) studied by S K-XAFS and S-1s XPS
journal, May 1996

Surface Extended X-Ray-Absorption Fine Structure of Low- Z Adsorbates Studied with Fluorescence Detection
journal, September 1985

Thiophene chemisorption and thermal decomposition on nickel(100) single-crystal surfaces
journal, July 1987

Initial steps in the desulfurization of thiophene/Ni(100)—A DFT study
journal, March 2003

Adsorption of thiophene on Ni(100), Cu(100), and Pd(100) surfaces: ab initio periodic density functional study
journal, February 2004

DFT study of adsorption and dissociation of thiophene molecules on Ni(110)
journal, August 2003

Projector augmented-wave method
journal, December 1994

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Methods of conjugate gradients for solving linear systems
journal, December 1952

  • Hestenes, M. R.; Stiefel, E.
  • Journal of Research of the National Bureau of Standards, Vol. 49, Issue 6
  • DOI: 10.6028/jres.049.044

Solution of Schrödinger’s equation for large systems
journal, December 1989

  • Teter, Michael P.; Payne, Michael C.; Allan, Douglas C.
  • Physical Review B, Vol. 40, Issue 18
  • DOI: 10.1103/PhysRevB.40.12255

A DFT study of the adsorption of thiophene on Ni(100)
journal, October 2001

Surface XAFS studies of adsorbate structure and bonding
journal, March 1995

Electronic Structure of an Organic/Metal Interface: Pentacene/Cu(110)
journal, October 2012

  • Müller, Kathrin; Seitsonen, Ari P.; Brugger, Thomas
  • The Journal of Physical Chemistry C, Vol. 116, Issue 44
  • DOI: 10.1021/jp308058u

Localisation of adsorbate-induced demagnetisation: CO chemisorbed on Ni{110}
journal, September 2000

CO Chemisorption on Ni(110): Effect on Surface Magnetism
journal, May 1986

Density-functional study of the adsorption of benzene on the (111), (100) and (110) surfaces of nickel
journal, January 2001

A grid-based Bader analysis algorithm without lattice bias
journal, January 2009

Improved grid-based algorithm for Bader charge allocation
journal, January 2007

  • Sanville, Edward; Kenny, Steven D.; Smith, Roger
  • Journal of Computational Chemistry, Vol. 28, Issue 5
  • DOI: 10.1002/jcc.20575

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Competing adsorption mechanisms of pyridine on Cu, Ag, Au, and Pt(110) surfaces
    journal, December 2018

    • Malone, Walter; von der Heyde, Johnathan; Kara, Abdelkader
    • The Journal of Chemical Physics, Vol. 149, Issue 21
    • DOI: 10.1063/1.5054788
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: