Abstract
The anomalous glass-like thermal conductivity of crystalline clathrates has been suggested to be the result of the scattering of thermal phonons of the framework by ‘rattling’ motions of the guests in the clathrate cages. Using the site-specific 83Kr nuclear resonant inelastic scattering spectroscopy in combination with conventional incoherent inelastic neutron scattering and molecular-dynamics simulations, we provide unambiguous evidence and characterization of the effects on these guest–host interactions in a structure-II Kr clathrate hydrate. The resonant scattering of phonons led to unprecedented large anharmonic motions of the guest atoms. The anharmonic interaction underlies the anomalous thermal transport in this system. Clathrates are prototypical models for a class of crystalline framework materials with glass-like thermal conductivity. The explanation of the unusual molecular dynamics has a wide implication for the understanding of the thermal properties of disordered solids and structural glasses.
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Acknowledgements
We thank T. Toellner, A. Said and A. Alatas of the Advanced Photon Source for their help during the experiment. Use of the Advanced Photon Source is supported by the US Department of Energy, Office of Basic Energy Sciences, Office of Science, under Contract no. W-31-109-ENG-38.
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Tse, J., Klug, D., Zhao, J. et al. Anharmonic motions of Kr in the clathrate hydrate. Nature Mater 4, 917–921 (2005). https://doi.org/10.1038/nmat1525
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DOI: https://doi.org/10.1038/nmat1525
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