Physical, Optical and Electron paramagnetic resonance studies of PbBr₂-PbO-B₂O₃glasses containing Cu²⁺ions

A comparable study of the EPR spectra and local structures for 3d1‐ and 3d9‐doped halo‐borate glasses

“…10,14 It is worth mentioning that EPR has been proved highly sensitive to the paramagnetic signals of these TM impurities, which has been adopted to investigate the PbX 2 -PbO-B 2 O 3 glasses (X = F, Cl, and Br) doped with Cu 2+ (3d 9 ), 7,15 represented by the properties of g factors and hyperfine structure parameters, that is, g // > g ⊥ and A // > A ⊥ for Cu 2+ . Despite the investigation of PbCl 2 -PbO-B 2 O 3 -CuO glasses in the previous article 16 and the rough explanation based on simple g formulae with various adjustable molecular orbital coefficients α 2 , β 2 , and β 1 2 , 12,13 the local structural information of paramagnetic impurities Cu 2+ in PbX 2 -PbO-B 2 O 3 glasses (X = F and Br) need to be further studied, which is helpful to acknowledge the role for different TM dopants (Cu 2+ and V 4+ ) by united and compared study. Accordingly, the EPR spectra of PbF 2 -PbO-B 2 O 3 -CuO and PbBr 2 -PbO-B 2 O 3 -CuO glasses have been studied by the perturbation method.…”

“…In PbX 2 -PbO-B 2 O 3 doped with CuO glasses, X usually represents halogen (e.g., F, Cl, and Br) ions. 10,12,13 Due to the Jahn-Teller effect, the structures around the dopants (Cu 2+ ) can be modified, characterized by distortions. 17,18 Despite the slightly different SPHs for PbX 2 -PbO-B 2 O 3 -CuO with different concentrations, the same properties g // > g ⊥ and | A // | > |A ⊥ | are satisfied at all concentrations, 10,12,13 which can be ascribed to the tetragonally elongated octahedral 3d 9 clusters 19,20 (see Figure 1).…”

“…To make an improved investigation from the previous simple g formulae based on various adjustable parameters (e.g., molecular orbital coefficients α 2 , β 2 , and β 1 2 in 12,13 ), the fourth-order perturbation formulae of SHPs for tetragonally elongated 3d 9 clusters are adopted here 18,19 :…”

“…To investigate the measured EPR spectra 12,13 and local structures for Cu 2+ 3) and listed in Table 1. Referring to the empirical relationship κ ≈ -2Nχ/ (3<r −3 >) and the values of core polarization constants for other Cu 2+ centers, 19,32,33 κ and H can be obtained in…”

“…Therefore, the comparable experiment has been carried out in Refs. [10][11][12][13], where the Cu 2+ and V 4+ ions are doped to better study the characteristics of oxyhalide glasses in optical conductors. This is because doping transition metal (TM) ions in materials usually can change the physical properties of the glasses, niobyl(3+) cation (NbO 3+ ), which enters deform dra (octahedra, tetragonal pyramids) with a co covalent bond to oxygen.…”