Skip to main content
SpringerLink
Log in

Kinetic analysis of the photochemically and thermally induced isomerization of an azobenzene derivative on Au(111) probed by two-photon photoemission

  • Published:
Applied Physics A Aims and scope Submit manuscript

Abstract

Two-photon photoemission (2PPE) spectroscopy is employed to quantify the photochemically and thermally induced trans ⇌ cis isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on an Au(111) surface. The isomerization of TBA is accompanied by significant changes in the electronic structure, namely different energetic positions of the lowest unoccupied molecular orbital of both isomers and the appearance of an unoccupied final state for cis-TBA. A quantitative analysis of these effects allows the calculation of cross sections for the reversible isomerization and determination of the ratio between both isomers in the photostationary state, where 55±5% of the molecules are switched to cis-TBA. The cross section for the photoinduced trans → cis isomerization is 3.3±0.5×10−22 cm2, while for the back reaction, a value of 2.7±0.5×10−22 cm2 is obtained. Furthermore a pronounced reduction of the activation energy by a factor of four compared to the free molecule is found for the thermally activated cis → trans isomerization of the surface-adsorbed TBA. This demonstrates that the potential energy landscape of the adsorbed TBA is remarkably different from the liquid phase.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. M. Irie (ed.), Photochromism: memories and switches. Chem. Rev. 100, 1683 (2000)

  2. B.L. Feringa, Molecular Switches (Wiley-VCH, Weinheim, 2001)

    Book  Google Scholar 

  3. M.R. Bryce, M.C. Petty, D. Bloor, Molecular Electronics (Oxford University Press, New York, 1995)

    Google Scholar 

  4. J.K. Gimzewski, C. Joachim, Science 238, 1683 (1999)

    Article  ADS  Google Scholar 

  5. C. Joachim, J.K. Gimzewski, A. Aviram, Nature 408, 541 (2000)

    Article  ADS  Google Scholar 

  6. Z. F Liu, K. Hashimoto, A. Fujishima, Nature 347, 658 (1990)

    Article  ADS  Google Scholar 

  7. T. Ikeda, O. Tsutsumi, Science 268, 1873 (1995)

    Article  ADS  Google Scholar 

  8. C. Zhang, M.-H. Du, H.-P. Cheng, X.-G. Zhang, A.E. Roitberg, J.L. Krause, Phys. Rev. Lett. 92, 158301 (2004)

    Article  ADS  Google Scholar 

  9. N. Tamai, O.H. Miyasaka, Chem. Rev. 100, 1875 (2000)

    Article  Google Scholar 

  10. H. Rau, in Photochromism—Molecules and Systems, ed. by H. Dürr, H. Bouas-Laurent (Elsevier, Amsterdam, 2003)

    Google Scholar 

  11. D. Fanghänel, G. Timpe, V. Orthman, in Organic Photochromes, ed. by A.V. El’tsov (Consultants Bureau, New York, 1990)

    Google Scholar 

  12. D. Dulic, S.J. van der Molen, T. Kudernac, H.T. Jonkman, J.J.D. de Jong, T.N. Bowden, J. van Esch, L.B. Feringa, J.B. van Wees, Phys. Rev. Lett. 91, 207402 (2003)

    Article  ADS  Google Scholar 

  13. B.-Y. Choi, S.-J. Kahng, S. Kim, H. Kim, H.W. Kim, Y.J. Song, J. Ihm, Y. Kuk, Phys. Rev. Lett. 96, 156106 (2006)

    Article  ADS  Google Scholar 

  14. J. Henzl, M. Mehlhorn, H. Gawronski, K.-H. Rieder, K. Morgenstern, Angew. Chem. Int. Ed. 45, 603 (2006)

    Article  Google Scholar 

  15. M. Alemani, M.V. Peters, S. Hecht, K.-H. Rieder, F. Moresco, L. Grill, J. Am. Chem. Soc. 128, 14446 (2006)

    Article  Google Scholar 

  16. S. Hagen, F. Leyssner, D. Nandi, M. Wolf, P. Tegeder, Chem. Phys. Lett. 444, 85 (2007)

    Article  ADS  Google Scholar 

  17. M.J. Comstock, N. Levy, A. Kirakosian, J. Cho, F. Lauterwasser, J.H. Harvey, D.A. Strubbe, J.M.J. Fréchet, D. Trauner, S.G. Louie, M.F. Crommie, Phys. Rev. Lett. 99, 038301 (2007)

    Article  ADS  Google Scholar 

  18. L. Óvári, M. Wolf, P. Tegeder, J. Phys. Chem. C 111, 15370 (2007)

    Article  Google Scholar 

  19. P.S. Kirchmann, P.A. Loukakos, U. Bovensiepen, M. Wolf, New J. Phys. 7, 113 (2005)

    Article  ADS  Google Scholar 

  20. P. Tegeder, S. Hagen, F. Leyssner, M.V. Peters, S. Hecht, T. Klamroth, P. Saalfrank, M. Wolf, Appl. Phys. A 88, 465 (2007)

    Article  ADS  Google Scholar 

  21. M. Alemani, PhD thesis, Freie Universität Berlin, 2007; http://www.diss.fu-berlin.de/2007/238/index.html

  22. M. Alemani, S. Selvanathan, F. Ample, M.V. Peters, K.-H. Rieder, F. Moresco, Ch. Joachim, S. Hecht, L. Grill, J. Phys. Chem. C 112, 10509 (2008)

    Article  Google Scholar 

  23. M.J. Comstock, N. Levy, J. Cho, L. Berbil-Bautista, M.F. Crommie, D.A. Poulsen, J.M.J. Fréchet, Appl. Phys. Lett. 92, 123107 (2008)

    Article  ADS  Google Scholar 

  24. S. Weigelt, C. Busse, L. Petersen, E. Rauls, B. Hammer, K.V. Gothelf, F. Besenbacher, T.R. Linderoth, Nat. Mater. 5, 112 (2006)

    Article  ADS  Google Scholar 

  25. P. Saalfrank, Universität Potsdam, private communication

  26. S. Hagen, P. Kate, F. Leyssner, D. Nandi, M. Wolf, P. Tegeder, (2008, submitted)

Download references

Author information

Authors and Affiliations

  1. Fachbereich Physik, Freie Universität Berlin, Arnimallee 14, 14195, Berlin, Germany

    Sebastian Hagen, Peter Kate, Martin Wolf & Petra Tegeder

  2. Department of Chemistry, Humboldt-Universität Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany

    Maike V. Peters & Stefan Hecht

Authors
  1. Sebastian Hagen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Peter Kate
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Maike V. Peters
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Stefan Hecht
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Martin Wolf
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Petra Tegeder
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Petra Tegeder.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hagen, S., Kate, P., Peters, M.V. et al. Kinetic analysis of the photochemically and thermally induced isomerization of an azobenzene derivative on Au(111) probed by two-photon photoemission. Appl. Phys. A 93, 253–260 (2008). https://doi.org/10.1007/s00339-008-4831-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00339-008-4831-5

PACS

Search

Navigation