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Structural and Dynamical Trends in Alkali-Metal Silanides Characterized by Neutron-Scattering Methods

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    Structural and Dynamical Trends in Alkali-Metal Silanides Characterized by Neutron-Scattering Methods
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    † NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States
    ‡ Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115, United States
    § National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    ∥ Laboratoire de Réactivité et Chimie des Solides (LRCS), UMR 7314 CNRS, Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens Cedex, France
    ⊥ Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
    *E-mail: [email protected]. Tel.: +1-301-975-8924.
    *E-mail: [email protected], [email protected]. Tel.: +1-301-975-0403.
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2016, 120, 38, 21218–21227
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    https://doi.org/10.1021/acs.jpcc.6b06591
    Published September 2, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH3, where M = K, Rb, Cs, K0.5Rb0.5, K0.5Cs0.5, and Rb0.5Cs0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (α) and ordered (β) phases for temperatures above and below about 200–250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a red shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order–disorder (β–α) phase transition, and measurements upon cooling of the α-phase revealed the known strong hysteresis for reversion back to the β-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH3– anions in the α- and β-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. This dynamical result might provide some insights concerning the enthalpy–entropy compensation effect previously observed for these potentially promising hydrogen storage materials.

    Copyright © 2016 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b06591.

    • Instructions for generating animations of all vibrational modes contributing to the simulated PDOSs; tables containing structural refinement results, experimental bending-mode energies, and DFT-generated phonon symmetries and energies, and figures showing the refinements (PDF)

    • CIF file for the NPD-refined structure of α-K0.5Cs0.5SiH3 (CIF)

    • CIF file for the NPD-refined structure of α-K0.5Rb0.5SiH3 (CIF)

    • CIF file for the NPD-refined structure of α-Rb0.5Cs0.5SiH3 (CIF)

    • CIF file for the NPD-refined structure of β-Rb0.5Cs0.5SiH3 (CIF)

    • CIF file for the NPD-refined structure of β-K0.5Cs0.5SiH3 (CIF)

    • Data files for generating animations of all vibrational modes contributing to the simulated PDOSs (ZIP)

    • Data files for generating animations of all vibrational modes contributing to the simulated PDOSs (ZIP)

    • Data files for generating animations of all vibrational modes contributing to the simulated PDOSs (ZIP)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2016, 120, 38, 21218–21227
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.6b06591
    Published September 2, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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