Abstract:
Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M0.923M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(egrbitals. There is a progressive increase in area of the edge peak from Fe0.923o Ni0.923nd Co0.923which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty egnt size=-1>βbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(eg S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM6uster), and is not a group (crystal energy band) effect.