具有旋转轨道自然过渡轨道的d块金属复合体的三重-单重发射
1Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY, 14260-3000, USA.
ChemistryOpen
|March 5, 2024
概括
旋转轨道自然过渡轨道 (SO-NTOs) 分析过渡金属复合体中的三重到单重排放. 该方法揭示了旋转禁止电子转换的强度源,补充了无旋转NTO分析.
科学领域:
- 量子化学是一种量子化学.
- 计算光谱学是一种计算光谱学.
- 无机化学 无机化学 无机化学
背景情况:
- 三重到单重的辐射对于理解过渡金属复合体中的光物理过程至关重要.
- 需要准确的理论方法来分析旋转禁止的电子转换.
研究的目的:
- 应用旋转轨道自然过渡轨道 (SO-NTO) 方法来分析过渡金属复合体中的三重到单重排放.
- 将SO-NTO与无旋转NTO进行比较,以描述这些转变.
主要方法:
- 应用SO-NTO方法来完成和限制活性空间 (CAS/RAS) 波函数计算.
- 在 [Ir(pbt) 2 ((acac) ], [Re(CO) 4 ((pbt) ], [W(CO) 4 ((bpy) ]和 [Mo(CO) 4 ((bpy) ] 复合体中分析了旋转禁止过渡.
- 旋转轨道和无旋转NTO的比较.
主要成果:
- SO-NTO方法被成功应用到研究三重到单重排放.
- 无旋转的NTO主要分配旋转禁止的过渡.
- SO-NTOs有效地确定了电子过渡强度的来源.
结论:
- SO-NTO 提供了关于旋转禁止过渡的强度的有价值的见解.
- SO-NTO和无旋转NTO分析的结合提供了对过渡金属复合体中的电子转换的全面了解.
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