The electronic energy structure of Ti-Ni and TiNi-Cu alloys has been studied experimentally by XPS and NEXAFS and theoretically by the full-potential local-orbital minimum-basis code. The study has revealed formation in the valence band of the Ti50Ni50 alloy of a common d-band through hybridization of the d-states of Ti with those of Ni, which is localized within a narrow binding-energy interval. This brings about an intra-atomic redistribution of Ti electron density in the Ti50Ni50 alloy compared to the pure metal: decrease of the occupancy of the Ti d-shell is countered by an increase in the number of Ti p-electrons. The occupancy of the Ti d-shell in the TiNi-Cu alloys, where Ni atoms are partially substituted by Cu, and in the Ti-Ni alloys with an excess of the Ni is more than in the equiatomic Ti50Ni50 alloy. The occupancy of the Ni and Cu d-shells in the Ti-Ni and TiNi-Cu alloys is independent of the atomic composition. The Ti d-shell sensitivity to variation of the nearest atomic environment is apparently due to their relatively itinerant behavior in the studied alloys. The results obtained suggest that the increase of the stiffness of an interatomic bond in the TiNi-Cu alloys with increasing Cu content and in the Ti-Ni alloys with increasing Ni content is possibly associated with the filling of Ti bonding d-states.
Influence of cationic substitution on the electronic-energy structure and optical properties of Cu2BIVS3(BIV=Si, Ge, Sn) compounds
