An XAS study of the local structure in Czochralski-grown optical scheelite-type sodium-gadolinium molybdates

The local environment of Mo6+ ions in the structures of scheelite-type crystals (space group I41/a) with the initial compositions (Na1/2Gd1/2)MoO4 (NGM 1:1) and (Na2/7Gd4/7□1/7)MoO4 (NGM 1:2; □ - vacancies) was determined by X-ray absorption spectroscopy (XAS) for the first time. Different coordination environments of Na1+ and Gd3+ ions caused primarily by the difference in their formal charges have been established based on the comparison of Mo–Gd and Mo–Na interatomic distances. According to resent results and structural data known for the (Na1-хREx)MO4 crystals (RE3+ = rare-earth cations), the character of distribution of different Na1+ and RE3+ polyhedra over NGM crystal structures is influenced by the sizes and electronegativities of Na1+, RE3+, and М6+ (M6+ = Mo, W) ions, the Na1+:RE3+ ratio, and vacancies in the M site. Disordered distribution of Na1+ and RE3+ polyhedra in NGM occurs without changing the symmetry of crystals (space group I41/a) and ordered one is accompanied by reduction of crystal symmetry.