1. Vibrational properties of β-KSiH3and β-RbSiH3: a combined Raman and inelastic neutron scattering study
- Author
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Carin Österberg, Ulrich Häussermann, Henrik Fahlquist, Yuan-Chih Lin, Terrence J. Udovic, Maths Karlsson, and János Mink
- Subjects
Phase transition ,Chemistry ,Phonon ,Anharmonicity ,Analytical chemistry ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Alkali metal ,01 natural sciences ,Inelastic neutron scattering ,0104 chemical sciences ,Ion ,symbols.namesake ,Libration ,symbols ,General Materials Science ,Atomic physics ,0210 nano-technology ,Raman spectroscopy ,Spectroscopy - Abstract
The hydrogen storage materials ASiH(3) (A=K and Rb) represent complex metal hydrides built from metal cations and pyramidal SiH3- ions. At room temperature, SiH3- moieties are randomly oriented because of dynamical disorder (-modifications). At temperatures below 200K, ASiH(3) exist as ordered low-temperature () modifications. The vibrational properties of -ASiH(3) were characterized by a combination of Raman spectroscopy and inelastic neutron scattering. Internal modes of SiH3- are observed in the spectral range 1800-1900cm(-1) (stretching modes) and 890-1000cm(-1) (bending modes). External modes are observed below 500cm(-1). Specifically, SiH3- librations are between 300-450cm(-1) and 270-400cm(-1) for A=K and Rb, respectively, SiH3- translations are between 95 and 160cm(-1), K+ translations are in the range 60-100cm(-1) and Rb+ translations in the range 50-70cm(-1). The red-shift of libration modes for A=Rb is associated with a 15-30% reduction of the libration force constants of SiH3- ions in -RbSiH3. This correlates with a lower temperature for the - order-disorder phase transition (278 vs 298K). Libration modes become significantly anharmonic with increasing temperature but are maintained up to at least 200K. The vibrational properties of ASiH(3) compare well to those of alkali metal borohydrides ABH(4) (A=Na-Cs).
- Published
- 2016
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