LiSc(BH 4 ) 4 has been prepared by ball milling of LiBH 4 and ScCl 3 . Vibrational spectroscopy indicates the presence of discrete Sc(BH 4 ) 4 -ions. DFT calculations of this isolated complex ion confirm that it is a stable complex, and the calculated vibrational spectra agree well with the experimental ones. The four BH 4 -groups are oriented with a tilted plane of three hydrogen atoms directed to the central Sc ion, resulting in a global 8 + 4 coordination. The crystal structure obtained by high-resolution synchrotron powder diffraction reveals a tetragonal unit cell with a ) 6.076 Å and c ) 12.034 Å (space group P-42c). The local structure of the Sc(BH 4 ) 4 -complex is refined as a distorted form of the theoretical structure. The Li ions are found to be disordered along the z axis.

IR and Raman data were obtained from R-, -, and mixed ( ,γ)-Ca(BH 4 ) 2 samples and from the deuterated ,γ phase mixture. The results obtained with R phase indicate that the DFT calculated values for the B-H stretching modes and the lattice vibrations are fairly close to the experimental values. The spectral behavior at temperatures around the transition to the phase shows a continuous transition and suggests the presence of disorder caused by reorientational motions of the [BH 4 ] -ion in the phase. The data indicate that there are more deformation bands observed for the mixed ( ,γ) samples than for the R phase which indicates structural variations between the and the γ phases.