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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvatochromic Shifts: A Reconsideration
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Solvatochromic Shifts: A Reconsideration

机译：Solvatochromic Shifts：重新思考

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摘要

Solvatochromic shifts in molecular spectra are often used to determine excited-state dipole moments. In comparing results with the more accurate gas-phase stark effects studies, large discrepancies are obtained in the few cases in which both types of studies have been carried out. We attempt to reconcile the two techniques by reanalyzing solvatochromic shift measurements in the situation in which a field-induced perturbation by a nearby state is possible. It is found that, in the high field limit, if we reinterpret solvatochromic shift studies as measuring an effective dipole moment which is a function of the dipole moments of both states and the transition moment between the two states, a possible explanation of the discrepancy is obtained. This is demonstrated to be reasonable in the only case (aniline) for which sufficient data are available. We also include examination of field-induced intensity borrowing as well as certain cavity-induced resonances and magnetic field induced effects. Finally we suggest some experiments to test the extent to which this reinterpretation is needed.
机译：分子光谱中的溶剂变色位移通常用于确定激发态偶极矩。在将结果与更准确的气相斯塔克效应研究进行比较时，在少数两种情况下均进行了两种研究的情况下，存在较大差异。我们试图通过重新分析溶剂变色位移测量来调和这两种技术，在这种情况下，可能会引起附近状态引起的场扰动。发现在高场极限下，如果我们将溶剂变色位移研究重新解释为测量有效偶极矩，该偶极矩是两个状态的偶极矩和两个状态之间的跃迁函数的函数，则可能是该差异的解释获得。在只有足够数据可用的唯一情况下（苯胺），这被证明是合理的。我们还包括检查磁场感应强度借用以及某些空腔感应共振和磁场感应效应。最后，我们建议进行一些实验来测试这种重新解释的程度。

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