Abstract
Proton transfer through hydrogen bonds plays a fundamental role in many physical, chemical and biological processes1,2,3,4,5. Proton dynamics is susceptible to quantum tunnelling, which typically involves many hydrogen bonds simultaneously, leading to correlated many-body tunnelling6,7,8,9. In contrast to the well-studied incoherent single-particle tunnelling, our understanding of many-body tunnelling is still in its infancy. Here we report the real-space observation of concerted proton tunnelling in a cyclic water tetramer using a cryogenic scanning tunnelling microscope. This is achieved by monitoring the reversible interconversion of the hydrogen-bonding chirality of the water tetramer with a chlorine-terminated scanning tunnelling microscope tip. We found that the presence of the Cl anion at the tip apex may either enhance or suppress the concerted tunnelling process, depending on the details of the coupling symmetry between the Cl ion and the protons. Our work opens up the possibility of controlling the quantum states of protons with atomic-scale precision.
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Acknowledgements
This work was supported by the National Basic Research Programs of China under Grant Nos 2012CB921303, 2012CB921304 and 2013CB934600, the National Science Foundation of China under Grant Nos 11104004, 11274012, 91021007, 91321309, 11290162/A040106 and 11275008. Y.J. acknowledges support from the National Program for Support of Top-notch Young Professionals. We are grateful for the computational resources provided by the supercomputer TianHe-1A in Tianjin, China. We thank Z. H. Cheng, A. H. Castro Neto, M. F. Crommie and A. Hodgson for enlightening discussions.
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Y.J. and E-G.W. designed and supervised the project. X.M., J.G. and Y.J. performed the STM measurements. J.C. and X-Z.L. carried out the DFT calculations. J.P., J.G., X.M., Z.W., and Y.J. analysed the data. J-R.S. contributed to the interpretation of the data. Y.J. and X.M. wrote the manuscript with J.G., J.P., J.C., X-Z.L. and E-G.W. The manuscript reflects the contributions of all authors.
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Meng, X., Guo, J., Peng, J. et al. Direct visualization of concerted proton tunnelling in a water nanocluster. Nature Phys 11, 235–239 (2015). https://doi.org/10.1038/nphys3225
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DOI: https://doi.org/10.1038/nphys3225
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