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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Orientational and Vibrational Relaxation Dynamics of Perylene and 1-Methylperylene in n-Alcohols: Probing the Balance between van der Waals and Hydrogen-Bonding Interactions.
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Orientational and Vibrational Relaxation Dynamics of Perylene and 1-Methylperylene in n-Alcohols: Probing the Balance between van der Waals and Hydrogen-Bonding Interactions.

机译：n和1-甲基per在n-醇中的取向和振动弛豫动力学：探索范德华力与氢键相互作用之间的平衡。

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摘要

We report on the rotational diffusion and vibrational population relaxation dynamics of perylene and 1-methylperylene in the primary normal alcohols methanol through n-decanol. The rotational diffusion dynamics of the two chrompohores are the same to within the experimental uncertainty for n-propanol through n-decanol. We observe a double exponential decay of the induced orientational anisotropy for 1-methylperylene in all of the alcohols and for perylene in n-propanol through n-decanol. These data are consistent with previous literature reports on perylene in high-viscosity solvents and on 1-methylperylene in n-alkanes longer than n-octane. These data also reveal a substantial difference in the behavior of perylene in n-alkanes and n-alkanols. Both chromphores reorient as oblate rotors in the n-alkanols, with the aspect ratio of the oblate ellipsoid describing their motion depending on the solvent aliphatic chain length. The vibrational population relaxation dynamics of the two probe molecules differ significantly, not only because of the difference in the nature of the solvent-solute coupling but also because of subtle differences in the organization of the solvent around the two chromophores. These data reflect the importance of solvent self-association in determining the local environments of these two chromophores.
机译：我们报告了normal和正丁醇在主要的正构醇甲醇中normal和1-甲基per的旋转扩散和振动种群弛豫动力学。对于正丙醇到正癸醇，这两个色谱基团的旋转扩散动力学都在实验不确定性范围内。我们观察到在所有醇中1-甲基per和通过正癸醇在正丙醇中in的诱导取向各向异性的双指数衰减。这些数据与关于高粘度溶剂中的per和长于正辛烷的正烷中的1-甲基methyl的先前文献报道一致。这些数据还揭示了per在正构烷烃和正构烷醇中的行为存在实质性差异。两种色谱在正构烷醇中均作为扁转子旋转，其扁椭圆形的长径比描述了它们的运动，取决于溶剂脂族链长。这两个探针分子的振动种群弛豫动力学存在显着差异，这不仅是由于溶剂-溶质偶联性质的差异，还因为两个发色团周围的溶剂的组织存在细微差异。这些数据反映了溶剂自缔合在确定这两个生色团的局部环境中的重要性。

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