Li2B12Si2: The First Ternary Compound in the System Li/B/Si: Synthesis, Crystal Structure, Hardness, Spectroscopic Investigations, and Electronic Structure

We present the synthesis, crystal structure, hardness, IR/Raman and UV/Vis spectra, and FP-LAPW calculations of the electronic structure of Li(2)B(12)Si(2), the first ternary compound in the system Li/B/Si. Yellow, transparent single crystals were synthesized from the elements in tin as solvent at 1500 degrees C in h-BN crucibles in arc-welded Ta ampoules. Li(2)B(12)Si(2) crystallizes orthorhombic in the space group Cmce (no. 64) with a=6.1060(6), b=10.9794(14), c=8.4050(8) A, and Z=4. The crystal structure is characterized by a covalent network of B(12) icosahedra connected by Si atoms and Li atoms located in interstitial spaces. The structure is closely related to that of MgB(12)Si(2) and fulfils the electron-counting rules of Wade and Longuet-Higgins. Measurements of Vickers (H(V)=20.3 GPa) and Knoop microhardness (H(K)=20.4 GPa) revealed that Li(2)B(12)Si(2) is a hard material. The band gap was determined experimentally and calculated by theoretical means. UV/Vis spectra revealed a band gap of 2.27 eV, with which the calculated value of 2.1 eV agrees well. The IR and Raman spectra show the expected oscillations of icosahedral networks. Theoretical investigations of bonding in this structure were carried out with the FP-LAPW method. The results confirm the applicability of simple electron-counting rules and enable some structural specialties to be explained in more detail.