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Directed long-range molecular migration energized by surface reaction

Nature Chemistry volume 3, pages 400–408 (2011)Cite this article

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Abstract

The recoil of adsorbates away (desorption) and towards (reaction) surfaces is well known. Here, we describe the long-range recoil of adsorbates in the plane of a surface, and accordingly the novel phenomenon of reactions occurring at a substantial distance from the originating event. Three thermal and three electron-induced surface reactions are shown by scanning tunnelling microscopy to propel their physisorbed ethylenic products across the rough surface of Si(100) over a distance of up to 200 Å before an attachment reaction. The recoil energy in the ethylenic products comes from thermal exoergicity or from electronic excitation of chemisorbed alkenes. We propose that the mechanism of migration is a rolling motion, because the recoiling molecule overcomes raised surface obstacles. Electronic excitation of propene causes directional recoil and often end-to-end inversion, suggesting cartwheeling. Ab initio calculations of the halogenation and electron-induced reactions support a model in which asymmetric forces between the molecule and the surface induce rotation and therefore migration.

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Figure 1: Thermal dissociation of dihaloethanes.
Figure 2: Electron-induced ethylene migration.
Figure 3: Radial and angular distributions of electron-induced ethylene migration at various temperatures.
Figure 4: Electron-induced migration of chemisorbed propene.
Figure 5: Bias dependence of distance distribution.
Figure 6: DFT calculations of thermal and electron-induced recoil of ethylene.

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Acknowledgements

The authors thank I. R. McNab for critical discussions and for DFT calculations. J.C.P. thanks the Natural Sciences and Engineering Research Council of Canada (NSERC), Photonics Research Ontario (PRO), an Ontario Centre of Excellence (OCE) and the Xerox Research Centre Canada (XRCC) for their support for this work. W.A.H. thanks the Royal Society of London for support. J.C.P. and W.A.H. also thank the Canadian Institute for Advanced Research (CIFAR) for support. A.Z.-K. is supported by an Ontario Post-Doctoral Fellowship.

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Authors and Affiliations

  1. Department of Chemistry and Institute for Optical Sciences, University of Toronto, 80 St George Street, Toronto, M5S 3H6, Ontario, Canada

    K. R. Harikumar, John C. Polanyi & Amir Zabet-Khosousi

  2. Surface Science Research Centre, University of Liverpool, Liverpool, L69 3BX, UK

    Piotr Czekala, Haiping Lin & Werner A. Hofer

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Contributions

K.R.H., J.C.P., and A.Z.-K. designed the research. K.R.H. and A.Z.-K. collected and analysed the experimental data. P.C., H.L. and W.A.H. performed the DFT and NEB calculations. All authors contributed to the manuscript.

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Correspondence to John C. Polanyi.

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Harikumar, K., Polanyi, J., Zabet-Khosousi, A. et al. Directed long-range molecular migration energized by surface reaction. Nature Chem 3, 400–408 (2011). https://doi.org/10.1038/nchem.1029

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