Coordination and valent state of nickel ions in beryl and chrysoberyl crystals

Abstract

We have studied the polarized optical absorption and the EPR spectra of Ni-doped beryls grown by hydrothermal, flux and gas-transport methods, and chrysoberyl grown by the Czochralski and flux methods. In beryls, three groups of bands belonging to three various Ni centres were distinguished by analysis of the absorption band intensities. The first group, bands with maximums at 21740 (E ⊥ c), 17240 (E || c) and 9260 (E ⊥ + || c), 7140 (E || + ⊥ c) cm⁻¹, are due to Ni³⁺ in octahedral Al³⁺ site. The second group is bands at 25640 (E ⊥ c), 22220 (E || c) and 13520 (E || + ⊥ c), 13160 (E ⊥+ || c) cm⁻¹ and 8930 (E ⊥ + || c), 7460 (E || c) cm⁻¹, which are caused by Ni²⁺ in octahedral Al³⁺ site. Weak wide bands at 17540 (E ⊥ c), 15500 (E || c) cm⁻¹ and 6580 (E || + ⊥ c), 5950 (E || c) cm⁻¹ are related to Ni²⁺ in tetrahedral Be²⁺ site. The occurrence of Ni ions in Be²⁺ site is proved by the EPR spectra of ^1VNi⁺ in γ-irradiated samples. According to the spectra of optical absorption of Ni-doped chrysoberyl, two types of Ni centres have been established: Ni³⁺ and Ni²⁺ ions in octahedral Al³⁺ sites. From the EPR spectra of the X-ray irradiated crystals BeAl₂O₄: Ni, it follows that 68% of Ni⁺ ions occupy octahedral Al³⁺ sites with mirror symmetry and 32% are in Al³⁺ sites with inversion symmetry. In the approximation of trigonal field with regard to Trees correction, the energy levels of Ni³⁺ and Ni²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is well explained in terms of the spin–orbit interaction.