Wong Z C, Fan W Y, Chwee T S, Sullivan Michael B
Institute of High Performance Computing, Agency for Science, Technology and Research (A*STAR), 1 Fusionopolis Way, 138632, Singapore.
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.
Phys Chem Chem Phys. 2017 Aug 9;19(31):21046-21057. doi: 10.1039/c7cp03418k.
Fluorescence lifetimes were evaluated using TD-DFT under different approximations for the emitting molecule and various exchange-correlation functionals, such as B3LYP, BMK, CAM-B3LYP, LC-BLYP, M06, M06-2X, M11, PBE0, ωB97, ωB97X, LC-BLYP*, and ωB97X* where the range-separation parameters in the last two functionals were tuned in a non-empirical fashion. Changes in the optimised molecular geometries between the ground and electronically excited states were found to affect the quality of the calculated lifetimes significantly, while the inclusion of vibronic features led to further improvements over the assumption of a vertical electronic transition. The LC-BLYP* functional was found to return the most accurate fluorescence lifetimes with unsigned errors that are mostly within 1.5 ns of experimental values.
在对发射分子采用不同近似以及各种交换相关泛函（如B3LYP、BMK、CAM - B3LYP、LC - BLYP、M06、M06 - 2X、M11、PBE0、ωB97、ωB97X、LC - BLYP和ωB97X）的情况下，利用含时密度泛函理论（TD - DFT）评估荧光寿命，其中最后两个泛函中的范围分离参数是以非经验方式调整的。发现基态和电子激发态之间优化分子几何结构的变化会显著影响计算寿命的质量，而包含振转特征相较于垂直电子跃迁假设能带来进一步改进。发现LC - BLYP*泛函给出的荧光寿命最准确，其无符号误差大多在实验值的1.5纳秒范围内。
