2017/04/27 by H. H. Otto, Hans Hermann Otto, Otto, Hans Hermann
Energy · Materials Science · Physics and Astronomy · #Crystal Structures and Properties #Iron oxide chemistry and applications #Mesoporous Materials and Catalysis #cond-mat.mtrl-sci #cond-mat.other #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.1705.00526
17 pages, 7 figures
arxiv created 2017/04/27 · arxiv updated 2017/05/02
It is reported on growth of mm-sized single-crystals of the low-dimensional S = 1/2 spin compound Cu6(Ge,Si)6O18.6H2O by a diffusion technique in aqueous solution. A route to form Si-rich crystals down to possibly dioptase, the pure silicate, is discussed. Further, the assignment of dd excitations from UV-VIS spectra of the hexahydrate and the fully dehydrated compound is proposed in comparison to dioptase and selected Cu(II) oxo-compounds using bond strength considerations. Non-doped cuprates as layer compounds show higher excitation energies than the title compound. However, when the antiferromagnetic interaction energy as Jzln(2) is taken into account for cuprates, a single linear relationship between the Dqe excitation energy and equatorial Cu(II)-O bond strength is confirmed for all compounds. A linear representation is also confirmed between 2A1g energies and a function of axial and equatorial Cu-O bond distances, when auxiliary axial bonds are used for four-coordinated compounds. The quotient Dt/Ds of experimental orbital energies deviating from the general trend to smaller values indicates the existence of H2O respectively Cl1- axial ligands in comparison to oxo-ligands, whereas larger Dt/Dqe values indicate missing axial bonds. The quotient of the excitation energy 2A1g by 2x2Eg-2B2g allows to check for correctness of the assignment and to distinguish between axial oxo-ligands and others like H2O or Cl1-. Some assignments previously reported were corrected.