DFT calculations of crystal-field parameters for the lanthanide ions in the LaCl3 crystal
DFT calculations of crystal-field parameters for the lanthanide ions in the LaCl3 crystal
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LaCl3 晶体中镧系离子晶体场参数的 DFT 计算
DOI：
10.1088/0953-8984/23/20/205502
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发表时间：
2011-05-25
影响因子：
2.7
通讯作者：
Zhang, Yongfan
中科院分区：
文献类型：
--
作者：
Ning, Lixin;Zhang, Lingyu;Zhang, Yongfan
本文采用基于密度泛函理论的无轨道嵌入方法，结合有效哈密顿方法，计算了LaCl3晶体中稀土离子的晶场参数。二阶和四阶循环流动参数的计算值与实验值吻合较好。结果表明，配体极化效应对二阶荧光参数的符号和大小起着至关重要的作用，而4f电子与配体之间的泡利斥力对四阶荧光参数的影响是重要的。通过研究Eu3+在KPb2Cl5晶体中两个不同的Pb2+位上的相对占位，说明了本方法的有效性。本文所讨论的计算方法和结果对于更好地理解和模拟含镧系中的CF效应是有用的。
We present herein a calculation of crystal-field (CF) parameters for the lanthanide ions in the LaCl3 crystal, using the density functional theory-based orbital-free embedding formalism in conjunction with the effective Hamiltonian method. The calculated values for the second-and fourth-rank CF parameters agree fairly well with the experimental data. It is found that the effect of ligand polarization plays a crucial role in determining the sign and magnitude of the second-rank CF parameters, while the effect of Pauli repulsion between 4f electrons and the ligands is important for the fourth-rank CF parameters. The usefulness of the present approach is illustrated by a study of the relative preference of Eu3+ occupation on the two distinct Pb2+ sites in the KPb2Cl5 crystal. The computational approach and results discussed in this work are useful for a better understanding and simulation of the CF effect in the lanthanide-containing systems.