Advertisement

The Atomic-Scale Motion of Thiophene on Cu(111)

  • Barbara A. J. LechnerEmail author
Chapter
  • 263 Downloads
Part of the Springer Theses book series (Springer Theses)

Abstract

Self-assembled monolayers of sulfur-containing heterocycles and linear oligomers-containing thiophene groups are widely employed in organic electronic applications. Here, the surface dynamics of thiophene on Cu(111) are investigated by helium-3 spin-echo spectroscopy and molecular dynamics simulations. Thiophene adsorbs on top sites and forms a covalent S-Cu bond. Two competing activated processes are observed, manifest in a kink in the Arrhenius plot: jump diffusion between adjacent top sites over a barrier of 59–62 meV and rotation around the S-Cu anchor point over a barrier of 17 \(\pm \) 2 meV. In addition, flapping between different tilt angles is observed. MD simulations of the diffusive motion reveal an exceptionally high friction coefficient of 5 \(\pm \) 2 \(\mathrm{ps}^{-1}\).

Keywords

Tilt Angle Bridge Site Jump Diffusion Uptake Curve Adsorption Geometry 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

References

  1. 1.
    G. Barbarella, M. Melucci, G. Sotgiu, The versatile thiophene: an overview of recent research on thiophene-based materials. Adv. Mater. 17, 1581–1593 (2005)CrossRefGoogle Scholar
  2. 2.
    P.K. Milligan, B. Murphy, D. Lennon, B.C.C. Cowie, M. Kadodwala, A complete structural study of the coverage dependence of the bonding of thiophene on Cu(111). J. Phys. Chem. B 105, 140–148 (2001)CrossRefGoogle Scholar
  3. 3.
    J.A. Rodriguez, J. Hrbek, Interaction of sulfur with well-defined metal and oxide surfaces: unraveling the mysteries behind catalyst poisoning and desulfurization, Acc. Chem. Res. 32, 9–719 (1999)CrossRefGoogle Scholar
  4. 4.
    A.K. Neyestanaki, F. Klingstedt, T. Salmi, D.Y. Murzin, Deactivation of postcombustion catalysts, a review. Fuel 83, 395–408 (2004)CrossRefGoogle Scholar
  5. 5.
    B.A.J. Lechner, M. Sacchi, A.P. Jardine, H. Hedgeland, W. Allison, J. Ellis, S.J. Jenkins, P.C. Dastoor, B.J. Hinch, Jumping, rotating and flapping: the atomic scale motion of thiophene on Cu (111). J. Phys. Chem. Lett. 4, 1953–1958 (2013)Google Scholar
  6. 6.
    V. Schomaker, L. Pauling, The electron diffraction investigation of the structure of benzene, pyridine, pyrazine, butadiene-1,3, cyclopentadiene, furan, pyrrole, and thiophene. J. Am. Chem. Soc. 61, 1769 (1939)CrossRefGoogle Scholar
  7. 7.
    B. Bak, D. Christensen, L. Hansen-Nygaard, J. Rastrup-Andersen, The structure of thiophene. J. Mol. Spectrosc. 7, 58–63 (1961)ADSCrossRefGoogle Scholar
  8. 8.
    J. Stöhr, J.L. Gland, E.B. Kollin, R.J. Koestner, A.L. Johnson, E.L. Muetterties, F. Sette, Desulfurization and structural transformation of thiophene on the Pt(111) surface. Phys. Rev. Lett. 53, 2161 (1984)ADSCrossRefGoogle Scholar
  9. 9.
    B.A. Sexton, A vibrational and TDS study of the adsorption of pyrrole, furan and thiophene on Cu(100): evidence for \(\pi \)-bonded and inclined species. Surf. Sci. 163, 99–113 (1985)ADSCrossRefGoogle Scholar
  10. 10.
    A. Imanishi, S. Yagib, T. Yokoyama, Y. Kitajima, T. Ohta, Structural and electronic properties of adsorbed C\(_4\)H\(_4\)S on Cu(100) and Ni(100) studied by S K-XAFS and S-1s XPS. J. Electron. Spectrosc. Relat. Phenom. 80, 151–154 (1996)CrossRefGoogle Scholar
  11. 11.
    J. Gaudioso, W. Ho, Single-molecule vibrations, conformational changes, and electronic conductivity of five-membered heterocycles. J. Am. Chem. Soc. 123, 10095–10098 (2001)CrossRefGoogle Scholar
  12. 12.
    N.V. Richardson, J.C. Campuzano, The adsorption of thiophene on a Cu(111) surface. Vacuum 31, 449–451 (1981)ADSCrossRefGoogle Scholar
  13. 13.
    A. Imanishi, T. Yokoyama, Y. Kitajima, T. Ohta, Structural and electronic properties of adsorbed thiophene on Cu(111) studied by S K-edge X-ray absorption spectroscopy. Bull. Chem. Soc. Jpn. 71, 831–835 (1998)CrossRefGoogle Scholar
  14. 14.
    P. Milligan, J. McNamarra, B. Murphy, B.C.C. Cowie, D. Lennon, M. Kadodwala, A NIXSW and NEXAFS investigation of thiophene on Cu(111). Surf. Sci. 412(413), 166–173 (1998)ADSCrossRefGoogle Scholar
  15. 15.
    Oerlikon Leybold Vacuum GmbH, Bonner Strasse 498 (Bayenthal), 50968 Cologne, Germany, http://www.oerlikon.com/leyboldvacuum
  16. 16.
    Edwards Limited, Manor Royal, Crawley, West Sussex, RH10 9LW, United Kingdom, http://www.edwardsvacuum.com
  17. 17.
    P.R. Kole, H. Hedgeland, A.P. Jardine, W. Allison, J. Ellis, G. Alexandrowicz, Probing the non-pairwise interactions between CO molecules moving on a Cu(111) surface. J. Phys. Condens. Matter 24, 104016 (2012)ADSCrossRefGoogle Scholar
  18. 18.
    D. Farías, K.-H. Rieder, Atomic beam diffraction from solid surfaces. Rep. Prog. Phys. 61, 1575–1664 (1998)ADSCrossRefGoogle Scholar
  19. 19.
    P.A. Redhead, Thermal desorption of gases. Vacuum 12, 203 (1962)CrossRefGoogle Scholar
  20. 20.
    A.P. Jardine, H. Hedgeland, G. Alexandrowicz, W. Allison, J. Ellis, Helium-3 spin-echo: principles and application to dynamics at surfaces. Prog. Surf. Sci. 84, 323 (2009)ADSCrossRefGoogle Scholar
  21. 21.
    F.E. Tuddenham, H. Hedgeland, A.P. Jardine, B.A.J. Lechner, B.J. Hinch, W. Allison, Lineshapes in quasi-elastic scattering from species hopping between non-equivalent surface sites. Surf. Sci. 604, 1459–1475 (2010)ADSCrossRefGoogle Scholar
  22. 22.
    S. Paterson, W. Allison, H. Hedgeland, J. Ellis, A.P. Jardine, Rotation and translational motion prior to self-assembly: dynamics of ethanethiolate on Cu(111). Phys. Rev. Lett. 106, 256101 (2011)ADSCrossRefGoogle Scholar
  23. 23.
    S. Paterson, C.J. Aas, A.P. Jardine, Quasi-elastic lineshapes for atoms and simple molecules undergoing jump rotation on surfaces. Surf. Sci. 606, 426–434 (2012)ADSCrossRefGoogle Scholar
  24. 24.
    C.T. Chudley, R.J. Elliot, Neutron scattering from a liquid on a jump diffusion model. Proc. Phys. Soc. 77(2), 353–361 (1960)ADSCrossRefGoogle Scholar
  25. 25.
    P.G. De Gennes, Liquid dynamics and inelastic scattering of neutrons. Physica 25, 825–839 (1959)ADSCrossRefGoogle Scholar
  26. 26.
    S.J. Clark, M.D. Segall, C.J. Pickard, P.J. Hasnip, M.J. Probert, K. Refson, M. Payne, First principles methods using CASTEP. Z. Kristallogr. 220, 567 (2005)CrossRefGoogle Scholar
  27. 27.
    A. Tkatchenko, M. Scheffler, Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys. Rev. Lett. 102, 073005 (2009)ADSCrossRefGoogle Scholar
  28. 28.
    G. Alexandrowicz, P.R. Kole, E.Y.M. Lee, H. Hedgeland, R. Ferrando, A.P. Jardine, W. Allison, J. Ellis, Observation of uncorrelated microscopic motion in a strongly interacting adsorbate system. J. Am. Chem. Soc. 130, 6789–6794 (2008)CrossRefGoogle Scholar
  29. 29.
    G. Alexandrowicz, A.P. Jardine, H. Hedgeland, W. Allison, J. Ellis, Onset of 3D collective surface diffusion in the presence of lateral interactions: Na/Cu(001). Phys. Rev. Lett. 97, 156103 (2006)ADSCrossRefGoogle Scholar
  30. 30.
    H. Hedgeland, P.R. Kole, H. Davies, A.P. Jardine, G. Alexandrowicz, W. Allison, J. Ellis, G. Fratesi, G. Brivio, Surface dynamics and friction of K/Cu(001) characterized by helium-3 spin-echo and density functional theory. Phys. Rev. B 80, 1–7 (2009)Google Scholar
  31. 31.
    A.P. Jardine, G. Alexandrowicz, H. Hedgeland, R.D. Diehl, W. Allison, J. Ellis, Vibration and diffusion of Cs atoms on Cu(001). J. Phys. Condens. Matter 19, 305010 (2007)CrossRefGoogle Scholar
  32. 32.
    G. Alexandrowicz, A.P. Jardine, P. Fouquet, S. Dworski, W. Allison, J. Ellis, Observation of microscopic CO dynamics on Cu(001) using \(^3\)He spin-echo spectroscopy. Phys. Rev. Lett. 93, 156101–156103 (2004)ADSCrossRefGoogle Scholar
  33. 33.
    A.P. Jardine, H. Hedgeland, D. Ward, Y. Xiaoqing, W. Allison, J. Ellis, G. Alexandrowicz, Probing molecule-surface interactions through ultra-fast adsorbate dynamics: propane/Pt(111). New J. Phys. 10, 125026 (2008)ADSCrossRefGoogle Scholar
  34. 34.
    H. Hedgeland, P. Fouquet, A.P. Jardine, G. Alexandrowicz, W. Allison, J. Ellis, Measurement of single-molecule frictional dissipation in a prototypical nanoscale system. Nat. Phys. 5, 561 (2009)CrossRefGoogle Scholar
  35. 35.
    B.A.J. Lechner, A.S. de Wijn, H. Hedgeland, A.P. Jardine, B.J. Hinch, W. Allison, J. Ellis, Atomic scale friction of molecular adsorbates during diffusion. J. Chem. Phys. 138, 194710 (2013)ADSCrossRefGoogle Scholar
  36. 36.
    A.S. de Wijn, A. Fasolino, Relating chaos to deterministic diffusion of a molecule adsorbed on a surface. J. Phys. Condens. Matter 21, 264002 (2009)ADSCrossRefGoogle Scholar
  37. 37.
    A.S. de Wijn, Internal degrees of freedom and transport of benzene on graphite. Phys. Rev. E 84, 011610 (2011)ADSCrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2014

Authors and Affiliations

  1. 1.Materials Sciences DivisionLawrence Berkeley National LaboratoryBerkeleyUSA

Personalised recommendations