摘要
本文利用d^3-C_3~*强场能量矩阵的特征值、特征矢量以及相应的全组态混合EPR理论,系统地分析了镍氟硅水合物晶体的光学吸收谱及电子顺磁共振(EPR)谱.对NiSiF_6·6H_2O晶体,在每一温度下,利用一组光谱参量,首次协调一致地计算出了吸收谱的精细结构、基态自旋哈密顿参量及EPR条件(H,(?)).计算结果和观测值很好地一致.通过分析各晶场参量变化对ZFS随温度变化的影响,本文指出,在一定的近似下,只要适当假设三角畸变晶场参量α值随温度线性地变化,则基态ZFS参量D及顺磁g因子随温度变化的计算值可以较好地和观测结果一致。
By means of a complete configuration mixing EPR theory for cf—Civ complex ions and from the eigenvalues and eigenvectors of its complete configuration interaction strong field matrix for d^(?)-C_(3V), the optical and EPR spectra of the NiSiF_6·6H_2O crystals are analysed theoretically and systematically. Using only one set of spectral parameters for each temperature, the optical spectrum fine structure, the ground state spin-Hamiltonian parameters and the EPR conditions (H,ν) are calculated harmoniously and uniformly for the first time and the results are in quite good agreement with experiments. The theoretical analyses show that the temperature-dependence of the zero-field splitting parameter D and the paramagnetic g-factors can be attributed to the linear temperature- dependence of the trigonal field parameter a.
基金
国家自然科学基金
