Cu1-xHxZr2(PO4)3中Cu2+的EPR谱和局域结构研究

本文采用Cu²⁺斜方对称电子顺磁共振（EPR）参量的高阶微扰公式计算了晶体Cu_1-xH_xZr₂（PO₄）₃中Cu²⁺的EPR参量（g因子和超精细结构常数A因子）．计算结果表明，晶体Cu_1-xH_xZr₂（PO₄）₃中CuO₆]^10-基团的Cu-O键长分别为R_||≈0.241 nm，R_⊥≈0.215 nm，平面键角τ≈80.1°；由于对称性降低，中心金属离子基态²A_1g（θ）和²A_1g（ε）有一定程度混合，混合系数α≈0.995．所得EPR谱图的理论计算值与实验数据符合得很好．

A Theoretical Study of the EPR Spectra and Local Structures of Cu2+ Center in Cu1-xHxZr2(PO4)3

Electron paramagnetic resonance (EPR) parameters (i.e., g factor and hyperfine structure constant A) of the Cu²⁺ centers in Cu_1-xH_xZr₂(PO₄)₃ were simulated theoretically using high-order perturbation formulas for Cu²⁺ in rhombically elongated octahedra. The Cu-O bond-lengths of theCuO₆]^10- cluster in the Cu_1-xH_xZr₂(PO₄)₃ crystal were found to be R_|| ≈ 0.241 nm and R_⊥ ≈ 0.215 nm. The plane bond angle was τ ≈ 80.1°. Because of reduced symmetry, the ground state wave function exhibited admixtures between ²A_1g(θ) and ²A_1g(ε) with a mixing coefficient α≈0.995. The calculated EPR parameters showed good agreement with the experimental data.