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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Chimeric Behavior of Excited Thioxanthone in Protic Solvents: II. Theory
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Chimeric Behavior of Excited Thioxanthone in Protic Solvents: II. Theory

机译：质子溶剂中激发噻吨酮的嵌合行为：II。理论

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摘要

The chimeric behavior of thioxanthone in protic solvents has been investigated employing computational chemistry methods. In particular, methanol and 2,2,2-trifluoroethanol have been chosen in this study. The solvent environment has been modeled using microsolvation in combination with a conductor-like screening model. The vertical excitation spectrum within the same solvent is seen to depend on the number of specific bonds formed between the chromophore and the solvent molecules. Two different models have been discussed in this work, namely, one and two H-bond models. In particular, the formation of the second H-bond causes the energy gap between the pi(H)pi(L)* and n(O)pi(L)* states to increase further. Excited-state absorption spectra for the photophysically relevant electronic states have been theoretically determined for comparison with the time-resolved spectra recorded experimentally [Villnow, T.; Ryseck, G.; Rai-Constapel, V.; Marian, C. M.; Gilch, P. J. Phys. Chem. A 2014]. The equilibration of the (1)(pi(H)pi(L)*) and (3)(n(O)pi(L)*) states holds responsible for the chimeric behavior. This equilibrium sets in with a calculated time constant of 23 ps in methanol and 14 ps in TFE (5 and 10 ps in experiment, respectively). The radiative decay from the optically bright (1)(pi(H)pi(L)*) state is computed to occur with a time constant of 25 ns in both solvents (1425 ns in experiment).
机译：已使用计算化学方法研究了噻吨酮在质子溶剂中的嵌合行为。特别地，在该研究中选择了甲醇和2,2,2-三氟乙醇。使用微溶剂结合导体样的筛选模型对溶剂环境进行了建模。可以看到，同一溶剂中的垂直激发光谱取决于生色团与溶剂分子之间形成的特定键的数量。在这项工作中讨论了两个不同的模型，即一个和两个H键模型。特别地，第二氢键的形成导致pi（H）pi（L）*和n（O）pi（L）*状态之间的能隙进一步增大。理论上已经确定了与光物理相关的电子态的激发态吸收光谱，以便与实验记录的时间分辨光谱进行比较[Villnow，T .; Ryseck，G .; Rai-Constapel，V .;玛丽安·C·M; Gilch，P.J.Phys。化学2014]。 （1）（pi（H）pi（L）*）和（3）（n（O）pi（L）*）状态的平衡对嵌合行为负责。该平衡以在甲醇中23 ps和在TFE中14 ps的计算时间常数开始（实验中分别为5 ps和10 ps）。计算出在两种溶剂中，光学亮（1）（pi（H）pi（L）*）状态产生的辐射衰减的时间常数为25 ns（实验中为1425 ns）。

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