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H-atom relay reactions in real space

Nature Materials volume 11, pages 167–172 (2012)Cite this article

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Abstract

Hydrogen bonds are the path through which protons and hydrogen atoms can be transferred between molecules. The relay mechanism, in which H-atom transfer occurs in a sequential fashion along hydrogen bonds, plays an essential role in many functional compounds. Here we use the scanning tunnelling microscope to construct and operate a test-bed for real-space observation of H-atom relay reactions at a single-molecule level. We demonstrate that the transfer of H-atoms along hydrogen-bonded chains assembled on a Cu(110) surface is controllable and reversible, and is triggered by excitation of molecular vibrations induced by inelastic tunnelling electrons. The experimental findings are rationalized by ab initio calculations for adsorption geometry, active vibrational modes and reaction pathway, to reach a detailed microscopic picture of the elementary processes.

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Figure 1: Sequential STM images of the assembly process of the H2O–(OH)2 chain from individual water molecules on Cu(110).
Figure 2: Assembled water-hydroxyl chains showing H-atom transfer reactions.
Figure 3: Yields (rate) of H-atom transfer reactions as a function of voltage, current and position of electron injection.
Figure 4: Calculated potential energy surface for the H-atom relay reaction in an H2O–(OH)2 chain along the [001] direction.

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Acknowledgements

We thank the Supercomputer Center, Institute for Solid State Physics, University of Tokyo, and the Information Technology Center, University of Tokyo, for the use of the facilities. H.O. was supported in part by the Grant-in-Aid for Scientific Research on Priority Areas ‘Molecular Science for Supra Functional Systems’ from the Ministry of Education, Culture, Sports, Science and Technology, Japan. I.H. was supported by the Grant-in-Aid from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan (No. 21740228). H.U. was supported by the Grant-in-Aid for Scientific Research B (No. 18340085) from the Japan Society for the Promotion of Science (JSPS). T.K. acknowledges the support of the JSPS.

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Author notes

  1. T. Kumagai

    Present address: Present address: Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany,

Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan

    T. Kumagai, A. Shiotari, H. Okuyama, S. Hatta & T. Aruga

  2. JST CREST, Saitama 332-0012, Japan

    S. Hatta & T. Aruga

  3. WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

    I. Hamada

  4. Donostia International Physics Center (DIPC), 20018 San Sebastián, Spain

    T. Frederiksen

  5. Division of Nano and New Functional Materials, Graduate School of Science and Engineering, University of Toyama, Toyama 930-8555, Japan

    T. Frederiksen & H. Ueba

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Contributions

T.K. and H.O. designed and planned the experiments. T.K. and A.S. measured and analysed the STM data. I.H. performed the STATE calculations. T.F. performed the VASP calculations. H.O. supervised the project and H.U. provided guidance for the analysis completed by I.H. and T.F. All authors contributed to the discussion of the results. H.O., I.H., T.F. and H.U. wrote the paper.

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Correspondence to H. Okuyama.

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The authors declare no competing financial interests.

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Kumagai, T., Shiotari, A., Okuyama, H. et al. H-atom relay reactions in real space. Nature Mater 11, 167–172 (2012). https://doi.org/10.1038/nmat3176

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