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在晶体场与配位场理论的基础上,利用3d9离子在四角伸长八面体环境下的自旋哈密顿(spin Hamiltonian,SH)参量高阶微扰公式,计算了铅锌磷酸盐玻璃中掺杂Cu2+离子的SH参量,即g因子(g∥,g⊥)和超精细结构常数A因子(A∥, A⊥),在这些公式中同时考虑了配体轨道及旋轨耦合作用对该参量的贡献;采用重叠模型建立了杂质Cu2+离子局部结构参数与自旋哈密顿参量之间的关系;利用该离子的光吸收谱,通过拟合SH参量理论与实验值,获得了杂质中心[CuO6]10-基团的局域结构.计算结果表明,由于Jahn-Teller效应,[CuO6]10-团簇中沿着四次轴方向的键长R簇≈0.206 nm,而垂直方向键长R⊥≈0.202 nm,即该团簇具有四角伸长八面体的局部结构.基于上述局部结构关系所得的SH参量理论值接近于实验值.最后对上述结果的合理性进行了讨论.“,”Based on the crystal(ligand)field theory, the spin Hamiltonian(SH)parameters g-factors gi(i=∥,⊥)and the hyperfine structure constants Aifor Cu2+in lead zinc phosphate glass are theoretically studied by using the high-order perturbation formulae of these parameters for a 3d9ion in a tetragonally elongated octahed-ron.The ligand orbital and spin-orbit coupling interactions are involved in these formulas.The SH parameters are correlated with the local structure of the impurity center based on the superposition model.By fitting the cal-culated SH parameters for Cu2+in lead zinc phosphate glass to the experimental values, the local structure a-round the Cu2+center is obtained.According to the calculations,the ligand-impurity distances parallel and per-pendicular to the C4axis of the[CuO6]10-cluster are found to be,respectively,R簇≈0.206 nm and R⊥≈0.202 nm due to Jahn-Teller effect,exhibiting a tetragonal elongation distortion along C4axis.The theoretical results are close to the experimental values according to above studies.The validity of the calculated results is also dis-cussed.