【摘要】 本文对锕系化合物荧光光谱的实验研究进行了系统总结,并在此基础上重点介绍了锕酰(actinyl)化合物的电子结构以及荧光光谱模拟的原理。结合我们关于铀酰-甘氨酸水合物结构、稳定性和荧光光谱模拟的研究工作,本文对锕系化合物荧光光谱理论研究的现状、理论方法和计算结果进行了综述。铀酰配合物中O—U—O单元的对称伸缩振动决定了其荧光特征,通过理论研究,结合计算化学模拟,可以解释铀酰-甘氨酸水溶液中振动分辨的实验光谱图,并阐明热带(hot band)峰强度异常高的成因。上述研究结果表明,现代计算化学和实验技术相结合,能够用于深入地分析锕系化合物的结构、光谱和性质,包括溶剂配位层、生物配体的配位结构、热力学能量和荧光光谱等。更多还原

【Abstract】 In this mini-review,we have briefly summarized the experimental research on fluorescence spectra of actinide complexes,the electronic structures of actinyl complexes,and the basic principle for computational simulations of fluorescence spectra.Although numerous fluorescence spectroscopy data had been available experimentally,there were no theoretical investigations on vibrationally resolved fluorescence spectra of actinide complexes.Recently we have performed for the first time computational modeling of vibrationally resolved fluorescence spectra of uranyl complexes using Heller’s time-dependent theory for electronic spectroscopy.Herein reviewed are the theoretical results from computational chemistry modeling on the coordination structures,stabilization energies and fluorescence properties of uranyl-glycine-water complexes.Our research has shown that the vibrationally resolved electronic spectra and the unusually high intensity of the illustrious uranyl hot-band can be interpreted by combining state-of-the-art computational chemistry and contemporary experimental techniques.This integrated theory and experiment approach can lead to a detailed understanding of the geometries,energetics,and luminescence properties of actinide compounds,including those with bio-ligands.更多还原