Amsterdam Center for Multiscale Modeling, Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
J Phys Chem A. 2012 Jul 12;116(27):7397-404. doi: 10.1021/jp3011266. Epub 2012 Jun 29.
Four-component relativistic time-dependent density functional theory (TD-DFT) is used to study charge-transfer (CT) excitation energies of the uranyl molecule as well as the uranyl tetrachloride complex. Adiabatic excitation energies and vibrational frequencies of the excited states are calculated for the lower energy range of the spectrum. The results for TD-DFT with the CAM-B3LYP exchange-correlation functional for the UO(2)Cl(4) system are in good agreement with the experimentally observed spectrum of this species and agree also rather well with other theoretical data. Use of the global hybrid B3LYP gives qualitatively correct results, while use of the BLYP functional yields results that are qualitatively wrong due to the too low CT states calculated with this functional. The applicability of the overlap diagnostic of Peach et al. (J. Chem. Phys.2008, 128, 044118) to identify such CT excitations is investigated for a wide range of vertical transitions using results obtained with three different approximate exchange-correlation functionals: BLYP, B3LYP, and CAM-B3LYP.
采用四分量相对论含时密度泛函理论（TD-DFT）研究了铀酰分子以及铀酰四氯化物配合物的电荷转移（CT）激发能。计算了较低能谱范围内的绝热激发能和振动频率。对于[UO2Cl4]2-体系，采用 CAM-B3LYP 交换相关泛函的 TD-DFT 结果与该物种的实验观测光谱非常吻合，与其他理论数据也非常吻合。使用全局混合 B3LYP 可以得到定性正确的结果，而使用 BLYP 泛函由于该泛函计算的 CT 态太低，会得到定性错误的结果。使用 Peach 等人的重叠诊断（J. Chem. Phys.2008, 128, 044118）来识别这种 CT 激发的适用性，使用三种不同的近似交换相关泛函（BLYP、B3LYP 和 CAM-B3LYP）对广泛的垂直跃迁进行了研究。
