Cu1-xHxZr2(PO4)3中Cu2+的EPR谱和局域结构研究

doi:10.11938/cjmr20192787

摘要/Abstract

摘要： 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．

关键词: Cu_1-xH_xZr₂(PO₄)₃, 晶体场理论, 电子顺磁共振（EPR）, 局域结构

Abstract: 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 the[CuO₆]^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.

Key words: Cu_1-xH_xZr₂(PO₄)₃, crystal-field theory, electron paramagnetic resonance (EPR), local structure

中图分类号:

O737
O433

周梓发, 陈富, 张华明. Cu_1-xH_xZr₂(PO₄)₃中Cu²⁺的EPR谱和局域结构研究[J]. 波谱学杂志, 2020, 37(3): 399-406.

ZHOU Zi-fa, CHEN Fu, ZHANG Hua-ming. A Theoretical Study of the EPR Spectra and Local Structures of Cu²⁺ Center in Cu_1-xH_xZr₂(PO₄)₃[J]. Chinese Journal of Magnetic Resonance, 2020, 37(3): 399-406.

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Cu_1-xH_xZr₂(PO₄)₃中Cu²⁺的EPR谱和局域结构研究

A Theoretical Study of the EPR Spectra and Local Structures of Cu²⁺ Center in Cu_1-xH_xZr₂(PO₄)₃

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