Improvement of electronic structure calculations for the interpretation of the emission spectrum for NdIII complexes†

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2025-04-10 DOI:10.1039/D5CP00508F

Yolimar Gil, María José Maldonado, Ricardo Costa de Santana, Andrés Vega, Pablo Fuentealba and Daniel Aravena

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Abstract

A protocol to correct ab initio calculated luminescence spectra of Nd^III complexes is proposed. The emission spectrum of [Nd^III(bipy)(tta)₃] was measured to calibrate the optimal correction for the Racah parameters on top of a CASSCF calculation to attain the best energetic placement of the ⁴F_3/2 → ⁴I_13/2−9/2 emission lines. As interelectronic repulsion is the most important source of error in this calculation, this straightforward correction results in an accurate placement of transitions, allowing the assignment of a complex spectral shape in terms of its underlying transitions. Finally, the correction derived for [Nd^III(bipy)(tta)₃] was directly applied to a different Nd^III complex, demonstrating the broad use of this approach.

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改进了NdIII配合物发射光谱解释的电子结构计算

提出了一种修正NdIII配合物从头计算发光光谱的方法。测量了[NdIII(bipy)(tta)3]的发射光谱，在CASSCF计算的基础上校准了Racah参数的最佳校正，以获得4F3/2→4I13/2-9/2发射线的最佳能量位置。由于电子间排斥是这种计算中最重要的误差来源，这种直接的修正导致了准确的跃迁位置，允许根据其潜在的跃迁分配复杂的光谱形状。最后，将[NdIII(bipy)(tta)3]的修正结果直接应用于不同的NdIII复合体，证明了该方法的广泛应用

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.