Single-crystal structures of uranium and neptunium oxychalcogenides AnOQ (An=U, Np; Q=S, Se)

The compounds UOS, UOSe, NpOS, and NpOSe have been synthesized and their structures determined by means of single-crystal X-ray diffraction methods. The results provide more detailed crystallographic information, including more precise interatomic distances, than earlier determinations from powder diffraction data. These isostructural compounds adopt the PbFCl structure type. Each An atom is surrounded by four O and five Q atoms in a distorted monocapped square-antiprismatic arrangement.     

Bandgap narrowing in the layered oxysulfide semiconductor Ba_3Fe_2O_5Cu_2S_2: Role of FeO_2 layer

A new layered Cu-based oxychalcogenide Ba_3Fe_2O_5Cu_2S_2 has been synthesized and its magnetic and electronic properties were revealed. Ba_3Fe_2O_5Cu_2S_2 is built up by alternatively stacking [Cu_2S_2]~(2-) layers and iron perovskite oxide[(FeO_2)(BaO)(FeO_2)]~(2-)layers along the c axis that are separated by barium ions with Fe~(3+) fivefold coordinated by a square-pyramidal arrangement of oxygen. From the bond valence arguments, we inferred that in layered CuC h-based(Ch =S, Se, Te) compounds the +3 cation in perovskite oxide sheet prefers a square pyramidal site, while the lower valence cation prefers the square planar sites. The studies on susceptibility, transport, and optical reflectivity indicate that Ba_3Fe_2O_5Cu_2S_2 is an antiferromagnetic semiconductor with a Ne′el temperature of 121 K and an optical bandgap of 1.03 eV. The measurement of heat capacity from 10 K to room temperature shows no anomaly at 121 K. The Debye temperature is determined to be 113 K. Theoretical calculations indicate that the conduction band minimum is predominantly contributed by O 2p and 3 d states of Fe ions that antiferromagnetically arranged in FeO_2 layers. The Fe 3d states are located at lower energy and result in a narrow bandgap in comparison with that of the isostructural Sr_3Sc_2O_5Cu_2S_2.