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三坐标Au (I) 氨酸复合物的光激发状态中的Jahn-Teller扭曲
Khaldoon A Barakat1, Thomas R Cundari, Mohammad A Omary
1Department of Chemistry, University of North Texas, Denton, TX 76203-5070, USA.
Journal of the American Chemical Society
|November 20, 2003
概括
三坐标金(I) 氨酸复合体在激发状态下从三角形平面变为T形的结构变化. 这种Jahn-Teller扭曲解释了它们的发光和巨大的Stokes扭曲.
科学领域:
- 无机化学 无机化学
- 计算化学的计算化学
- 摄影化学的使用.
背景情况:
- 三坐标的[Au(PR3) 3+复合物以其光特性而闻名.
- 了解激发状态几何学对于解释它们的发光至关重要.
- 以前的模型经常假设激发状态的基态几何,限制了解释.
研究的目的:
- 为了计算优化三坐标[Au(PR3) 3+复合体的光激发状态.
- 为了阐明光刺激后的结构重排.
- 将计算结果与实验性紫外线吸收和可见辐射数据相关联.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 优化最低的三重发光激发状态进行了.
- 与基态几何和实验数据进行比较.
主要成果:
- 综合体从三角平面的基本状态重新排列到激发状态中的T形状.
- 这种T形扭曲因电子配置变化而被认定为Jahn-Teller效应.
- 计算的激发能量与实验性UV-Vis吸收和发射光谱一致.
结论:
- 这种T形兴奋状态几何学对于理解这些黄金复合物的发光是必不可少的.
- DFT计算准确地预测了兴奋状态结构和光谱特性.
- 这项研究澄清了这些光黄金复合体中巨大的斯托克斯移动的起源.
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