Theoretical studies of the local structures and EPR parameters for Cu$^{2+}$ center in Cd$_{2}$(NH$_{4}$)$_{2}$(SO$_{4}$)$_{3}$ single crystal

TL;DR

This paper uses theoretical models to interpret EPR parameters of Cu$^{2+}$ in a specific crystal, revealing local structural details and matching experimental data.

Contribution

It introduces a perturbation-based theoretical approach incorporating orbital admixture to accurately determine local structures and EPR parameters of Cu$^{2+}$ in the crystal.

Findings

Calculated local bond lengths for Cu$^{2+}$ in the crystal.

Good agreement between theoretical and observed EPR parameters.

Identified the influence of orbital admixture on EPR results.

Abstract

The electron paramagnetic resonance (EPR) parameters ($g$ factors $g_{i}$ and the hyperfine structure constants ${{A}}_{{i}}$, ${i} = {x}, {y}, {z}$) are interpreted by using the perturbation formulae for a $3{d}^{9}$ ion in rhombically ({D}$_{2h}$) elongated octahedra. In the calculated formulae, the crystal field parameters are set up from the superposition model, and the contribution to the EPR parameters from the admixture of $d$-orbitals in the ground state wave function of the Cu$^{2+}$ ion was taken into account. Based on the calculation, local structural parameters of the impurity Cu$^{2+}$ center in Cd$_{2}$(NH$_{4}$)$_{2}$(SO$_{4}$)$_{3}$ (CAS) crystal were obtained (i.e., ${R}_{{x}}\approx 2.05$ {\AA}, ${R}_{{y}} \approx 1.91$ {\AA}, ${R}_{{z}} \approx 2.32$ {\AA}). The theoretical EPR parameters based on the above Cu$^{2+}$-O$^{2-}$ bond lengths in CAS crystal show a good agreement with the observed values. The results are discussed.