Combined DFT and wave function theory approach to excited states of lanthanide luminescent materials: A case study of LaF3:Ce3+,Journal of the Chinese Chemical Society

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Combined DFT and wave function theory approach to excited states of lanthanide luminescent materials: A case study of LaF3:Ce3+
Journal of the Chinese Chemical Society ( IF 1.6 ) Pub Date : 2022-09-18 , DOI: 10.1002/jccs.202200348
Huai‐Yang Sun ₁ , Hong Jiang ₁

Affiliation

Lanthanide luminescent materials play key roles in modern society, but their first-principles treatment remains a great challenge due to complex manifold of electronic excited states and the difficulty in performing excited state structural relaxations that is necessary to model luminescent properties. Herein, we propose a practical approach that combines embedded cluster model (ECM) based multi-configurational wave function theory (WFT) and occupancy constrained density-functional theory plus the Hubbard U correction (OC-DFT + U) to treat lanthanide doped luminescent materials, using LaF₃:Ce³⁺, a typical scintillator with low symmetry, as a case study. We show that the combined approach yields accurate absorption energies with an error on the order of 200 cm⁻¹, but the emission energies are significantly underestimated, the origin of which is further clarified by vibrationally resolved absorption and emission spectra calculation. This work demonstrates the possibility of combining ECM-based wave function theory and periodic DFT into a comprehensive computational scheme for lanthanide luminescent materials and highlights the limitations of the current implementation of OC-DFT + U for excited state structural optimization.

中文翻译：

镧系元素发光材料激发态的组合 DFT 和波函数理论方法：以 LaF3:Ce3+ 为例

镧系发光材料在现代社会中发挥着关键作用，但由于电子激发态的复杂流形以及难以执行模拟发光特性所必需的激发态结构弛豫，其第一性原理处理仍然是一个巨大的挑战。在此，我们提出了一种结合基于嵌入式簇模型 (ECM) 的多配置波函数理论 (WFT) 和占用约束密度泛函理论以及哈伯德 U 校正 (OC-DFT + U) 来处理镧系元素掺杂发光材料的实用方法, 使用 LaF ₃ :Ce ³⁺，一个典型的低对称性闪烁体，作为案例研究。^{我们表明，组合方法产生准确的吸收能量，误差在 200 cm -1}左右，但发射能量被显着低估，其来源通过振动分辨吸收和发射光谱计算进一步阐明。这项工作证明了将基于 ECM 的波函数理论和周期性 DFT 结合到镧系元素发光材料的综合计算方案中的可能性，并强调了当前实施 OC-DFT + U激发态结构优化的局限性。

更新日期：2022-09-18

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