A SYSTEMATIC ANALYSIS OF THE SPECTRA OF TRIVALENT ACTINIDE CHLORIDES IN D3H SITE SYMMETRY
A SYSTEMATIC ANALYSIS OF THE SPECTRA OF TRIVALENT ACTINIDE CHLORIDES IN D3H SITE SYMMETRY
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DOI：
10.1063/1.462278
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发表时间：
1992-06-15
影响因子：
4.4
通讯作者：
CARNALL, WT
中科院分区：
文献类型：
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作者：
CARNALL, WT
用5f（N）组态跃迁解释了化合物AnCl_3和LaCl_3单晶中锕系离子的光谱。能级计算采用有效算符哈密顿量，其参数由拟合实验数据确定。假设近似的D3 h位点对称性，原子和晶体场矩阵同时对角化。光谱数据取自文献，但在大多数情况下，补充了未发表的测量吸收和荧光。对每个离子的数据进行独立分析，然后对模型参数进行相互比较，并在许多情况下进行调整，以便在最终拟合过程中，主要相互作用随原子序数的增加而显示出参数值的一致趋势。与LaCl3和LaF3中镧系元素离子的光谱分析一致，在5f（N）系列的中心附近发现某些晶体场参数的幅度的突然变化。这导致了两组参数值，但两个系列的一半具有一致的趋势，并且观察到的能量和计算的能量之间通常非常好的一致性。一个新的能级图的基础上计算的晶体场能级能量为每个三价锕系离子已准备就绪。
The optical spectra of actinide ions in the compound AnCl3 and doped into single-crystal LaCl3 were interpreted in terms of transitions within 5f(N) configurations. Energy-level calculations were carried out using an effective-operator Hamiltonian, the parameters of which were determined by fitting experimental data. Atomic and crystal-field matrices were diagonalized simultaneously assuming an approximate D3h site symmetry. Spectroscopic data were taken from the literature but in most cases supplemented by unpublished measurements in absorption and in fluorescence. Data for each ion were analyzed independently, then the model parameters were intercompared and in many cases adjusted such that in the final fitting process the principal interactions showed uniform trends in parameter values with increasing atomic number. Consistent with analyses of the spectra of lanthanide ions in both LaCl3 and LaF3, abrupt changes in magnitude of certain crystal-field parameters were found near the center of the 5f(N) series. This resulted in two groups of parameter values, but with consistent trends for both halves of the series, and generally very good agreement between observed and computed energies. A new energy-level chart based on computed crystal-field level energies for each trivalent actinide ion has been prepared.