Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach
Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach
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DOI：
10.1063/1.2757168
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发表时间：
2007-08-21
影响因子：
4.4
通讯作者：
Barone, Vincenzo
中科院分区：
文献类型：
--
作者：
Improta, Roberto;Scalmani, Giovanni;Barone, Vincenzo
在可极化连续模型（PCM）的框架下，发展了一种在含时密度泛函理论（TD-DFT）计算中考虑溶剂效应的状态特异性（SS）模型。新模型允许在溶液中的荧光和磷光光谱的计算中的动态溶剂效应的严格和有效的治疗，它可以用于研究不同的弛豫时间制度。SS和传统的线性响应（LR）模型进行了比较，通过计算不同的基准系统（甲醛在水中和三个香豆素衍生物在乙醇中）的排放能量。特别注意动态溶剂化效应的影响LR几何优化的解决方案。甲醛的结果指出LR和SS方法的互补性和后者模型的优点，特别是对于极性溶剂和/或弱过渡。香豆素衍生物的计算的发射能量是非常接近他们的实验同行，指出了一个适当的治疗的重要性，非平衡溶剂的影响，激发态和基态能量。SS-PCM/TD-DFT模型的吸收和发射过程的研究的可用性允许在溶液中的一些不同的光谱特性的一致的治疗。(c)2007年，美国物理学会。
A state specific (SS) model for the inclusion of solvent effects in time dependent density functional theory (TD-DFT) computations of emission energies has been developed and coded in the framework of the so called polarizable continuum model (PCM). The new model allows for a rigorous and effective treatment of dynamical solvent effects in the computation of fluorescence and phosphorescence spectra in solution, and it can be used for studying different relaxation time regimes. SS and conventional linear response (LR) models have been compared by computing the emission energies for different benchmark systems (formaldehyde in water and three coumarin derivatives in ethanol). Special attention is given to the influence of dynamical solvation effects on LR geometry optimizations in solution. The results on formaldehyde point out the complementarity of LR and SS approaches and the advantages of the latter model especially for polar solvents and/or weak transitions. The computed emission energies for coumarin derivatives are very close to their experimental counterparts, pointing out the importance of a proper treatment of nonequilibrium solvent effects on both the excited and the ground state energies. The availability of SS-PCM/TD-DFT models for the study of absorption and emission processes allows for a consistent treatment of a number of different spectroscopic properties in solution. (c) 2007 American Institute of Physics.