Origin of the large anharmonicity in the phonon modes of LiBH4

•IR, Raman, and INS spectroscopy data and corresponding DFT-calculations on LiBH4.•Mismatch between experiment and theory are due to anharmonicity.•Strong anharmonic effects can be expected for vibrations with high H amplitude.

The dynamics and bonding of the complex hydride LiBH4 have been investigated by vibrational spectroscopy and density functional theory (DFT). The combination of infrared, Raman, and inelastic neutron-scattering (INS) spectroscopies on hydrided and deuterated samples reveals a complete picture of the dynamics of the BH4− ions as well as of the lattice. Particular emphasis is laid on a comparison between experiment and theory, revealing significant discrepancy between the two approaches for vibrations with high anharmonicity, which is related to large vibrational amplitudes. The latter is typical for librational modes in molecular crystals and pseudo-ionic crystals such as complex hydrides. The presented strategy for anharmonic frequency corrections might thus be generally applicable for this kind of materials.

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