Investigations on the EPR parameters and tetragonal distortions for Cu²⁺in alkali lead tetraborate glasses

Abstract

The electron paramagnetic resonance parameters (g factors and hyperfine structure constants) and local structures are theoretically investigated for Cu2+ in alkali lead tetraborate 90R2B4O7·9PbO·CuO (R = Li, Na and K) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 complex. The [CuO6]10− complexes are found to experience the relative tetragonal elongation ratios 18%, 23% and 30% for R = Li, Na and K, respectively, due to the Jahn–Teller effect, much larger than those for similar ARbB4O7 (A = Li, Na and K) glasses. This point is attributed to the lattice expansion (longer A–O bond lengths) with doped PbO, yielding lower force constants and more intense Jahn–Teller elongations in the 90R2B4O7·9PbO·CuO glasses. The increasing tendency (Li > Na > K) of the relative elongation ratio λ, covalency and the ratio Δg///Δg⊥ for g-shifts are systematically analysed in a uniform way.