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Theoretical Evidence of the Singlet Predominance in the Intramolecular Energy Transfer in Ruhemann's Purple Tb(III) Complexes
Advanced Theory and Simulations ( IF 2.9 ) Pub Date : 2021-02-10 , DOI: 10.1002/adts.202000304 Renaldo T. Moura 1 , Jhulie A. Oliveira 2 , Inácio A. Santos 2 , Ewerton M. Lima 1 , Luís D. Carlos 3 , Eduardo C. Aguiar 2 , Albano N. Carneiro Neto 3
Advanced Theory and Simulations ( IF 2.9 ) Pub Date : 2021-02-10 , DOI: 10.1002/adts.202000304 Renaldo T. Moura 1 , Jhulie A. Oliveira 2 , Inácio A. Santos 2 , Ewerton M. Lima 1 , Luís D. Carlos 3 , Eduardo C. Aguiar 2 , Albano N. Carneiro Neto 3
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This work presents a theoretical study on the geometries and intramolecular energy transfer (IET) process of Tb3+‐complexes based on the Ruhemman's purple (RP) as ligands. Density functional theory and its time‐dependent extension are performed to examine the coordination energies and excited states using the ωB97X‐D3/MWB54/def2‐TZVP/polarizable continuum model level of theory. The inclusion of solvent effect causes a blueshift in all excitation energies, which is crucial for a better description of the electronic situations of RP isomers and coordination compounds. The IET rates are assessed for 18 Tb‐RP different compounds, each one with 44 IET pathways, also, it is obtained that the main energy transfer channel comes from the singlet state, in complete agreement with previous experimental data. The energy transfer from the singlet state is mainly composed of the nonradiative absorptions 7F6→5G6 and 7F5→5G5, representing together 97% of the total IET rate. As far as it is known, this is the first time that the solvent effect is included in the IET rates calculation, registering a step toward the development of IET analysis without any experimental or phenomenological input data.
中文翻译：
Ruhemann紫色Tb（III）配合物中分子内能量转移中单重态占优势的理论证据
这项工作提出了关于Tb 3+的几何形状和分子内能量转移（IET）过程的理论研究-以Ruhemman紫色（RP）为配体的络合物。使用ωB97X-D3/ MWB54 / def2-TZVP /可极化连续体模型理论水平，通过密度泛函理论及其随时间的扩展来检查配位能和激发态。包含溶剂效应会导致所有激发能发生蓝移，这对于更好地描述RP异构体和配位化合物的电子状态至关重要。对18种Tb-RP不同化合物的IET速率进行了评估，每种化合物都有44条IET途径，并且还获得了主要的能量传递通道来自单重态，与之前的实验数据完全一致。从单重态的能量转移主要由非辐射吸收7 F 6 →5 G 6和7 F 5 → 5 G 5，总共占IET总数的97％。据了解，这是首次在IET速率计算中包括溶剂效应，这是向没有任何实验或现象学输入数据的IET分析发展迈出的一步。
更新日期：2021-03-09
中文翻译：
Ruhemann紫色Tb（III）配合物中分子内能量转移中单重态占优势的理论证据
这项工作提出了关于Tb 3+的几何形状和分子内能量转移（IET）过程的理论研究-以Ruhemman紫色（RP）为配体的络合物。使用ωB97X-D3/ MWB54 / def2-TZVP /可极化连续体模型理论水平，通过密度泛函理论及其随时间的扩展来检查配位能和激发态。包含溶剂效应会导致所有激发能发生蓝移，这对于更好地描述RP异构体和配位化合物的电子状态至关重要。对18种Tb-RP不同化合物的IET速率进行了评估，每种化合物都有44条IET途径，并且还获得了主要的能量传递通道来自单重态，与之前的实验数据完全一致。从单重态的能量转移主要由非辐射吸收7 F 6 →5 G 6和7 F 5 → 5 G 5，总共占IET总数的97％。据了解，这是首次在IET速率计算中包括溶剂效应，这是向没有任何实验或现象学输入数据的IET分析发展迈出的一步。
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