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The structure and reorientational dynamics of KB 3 H 8 were studied by using quasielastic and inelastic neutron scattering, Raman spectroscopy, first-principles calculations, differential scanning calorimetry, and in situ synchrotron radiation powder X-ray diffraction. The results reveal the existence of a previously unknown polymorph in between the α'- and β-polymorphs. Furthermore, it was found that the [B 3 H 8 ] - anion undergoes different reorientational motions in the three polymorphs α, α', and β. In α-KB 3 H 8 , the [B 3 H 8 ] - anion performs 3-fold rotations in the plane created by the three boron atoms, which changes to a 2-fold rotation around the C  2 symmetry axis of the [B 3 H 8 ] - anion upon transitioning to α'-KB 3 H 8 . After transitioning to β-KB 3 H 8 , the [B 3 H 8 ] - anion performs 4-fold rotations in the plane created by the three boron atoms, which indicates that the local structure of β-KB 3 H 8 deviates from the global cubic NaCl-type structure. The results also indicate that the high reorientational mobility of the [B 3 H 8 ] - anion facilitates the K + cation conductivity, since the 2-orders-of-magnitude increase in the anion reorientational mobility observed between 297 and 311 K coincides with a large increase in K + conductivity.

Interplay between the Reorientational Dynamics of the B3H8– Anion and the Structure in KB3H8

Interplay between the Reorientational Dynamics of the B₃H₈^– Anion and the Structure in KB₃H₈