Metal valence states inEu0.7NbO3,EuNbO3,andEu2Nb5O9by TB-LMTO-ASA band-structure calculations and resonant photoemission spectroscopy

The electronic structures of ${\mathrm{Eu}}_{2}{\mathrm{Nb}}_{5}{\mathrm{O}}_{9},$ ${\mathrm{EuNbO}}_{3},$ and ${\mathrm{Eu}}_{0.7}{\mathrm{NbO}}_{3}$ have been investigated by photoemission and total-yield spectroscopy with synchrotron radiation, and in the case of ${\mathrm{Eu}}_{2}{\mathrm{Nb}}_{5}{\mathrm{O}}_{9}$ by tight-binding linear muffin-tin orbital (LMTO) band-structure calculations. A central question for reduced europium niobates is that of the valence of Eu and Nb. Both europium and niobium atoms can appear in different valence states so that various electronic configurations in the title compounds are possible. For this reason, the valence band was studied by the resonant Eu…

An Inorganic Double Helix Sheathing Alkali Metal Cations: ANb2P2S12(A=K, Rb, Cs), A Series of Thiophosphates Close to the Metal-Nonmetal Boundary-Chalcogenide Analogues of Transition-Metal Phosphate Bronzes?

The new quaternary niobium thiophosphates ANb 2 P 2 S 1 2 (A=K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A 2 S, P 2 S 5 , and S at 600-700°C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS 6 structure type in the tetragonal space group I42d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb 2 P 2 S 1 2 , a= 15.887(3) and c=13.132(3) A for RbNb 2 P 2 S 1 2 , and a=15.850(2) and c= 13.119(3) A for KNb 2 P 2 S 1 2 . Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb 2 S 1 2…

Electronic structure and positron states at vacancies in Si and GaAs