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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvatochromic Shifts Reconsidered: Field-Induced Mixing in the Nonlinear Region and Application to Indole
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Solvatochromic Shifts Reconsidered: Field-Induced Mixing in the Nonlinear Region and Application to Indole

机译：重新考虑溶剂变色：非线性区域中的场致混合及其在吲哚中的应用

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In previous work we showed that the observed discrepancy between gas-phase Stark effect measurements of excited-state dipole moments and those measured by solvatochromic shifts could be explained by possible intervention of a nearby excited state. Field-induced mixing of the two excited states causes solvent shifts that are linear in the high-field limit, where most solvent field studies are carried out, but the excited-state dipole moment must be replaced by an effective dipole moment. This effective moment is a combination of the excited-state dipole moments of both states as well as the transition moment between the two states. This new moment may have effects both on the solvent shifts observed and on the intensities. In the low-field gas-phase limit, the shifts are also linear but caused by the simple excited-state dipole moment. In the intermediate field region, the solvent shifts are expected to be decidedly nonlinear. The effective dipole moment is shown to be field-dependent near an avoided crossing of the two excited states, and this results in nonlinear behavior of the solvent reaction field. By identification of the onset of nonlinearity or, even better, by the fitting of the solvent shift observed to predicted expressions, the individual contributions to the effective dipole moment can be unraveled. We show how this theory can be applied to observed solvent shifts in the molecule indole, which has been observed throughout the nonlinear region. Consistent dipolar parameters that reconcile gas-phase and solution-phase results are obtained.
机译：在先前的工作中，我们表明，可以通过对附近激发态的可能干预来解释所观测到的激发态偶极矩的气相斯塔克效应测量值与溶剂变色位移测量值之间的差异。场致两种激发态的混合会导致在高场极限范围内发生线性线性的溶剂移动，在该场中进行了大多数溶剂场研究，但必须用有效偶极矩代替激发态偶极矩。该有效力矩是两个状态的激发态偶极矩以及两个状态之间的过渡力矩的组合。这个新的时刻可能会影响观察到的溶剂位移和强度。在低场气相极限下，位移也是线性的，但由简单的激发态偶极矩引起。在中间场区域中，预期溶剂的变化绝对是非线性的。有效偶极矩在两个激发态的避免交叉附近表现出与场有关，这导致溶剂反应场的非线性行为。通过识别非线性现象的开始，或者更好地通过观察到的溶剂位移与预测表达式的拟合，可以得出对有效偶极矩的各个贡献。我们展示了如何将此理论应用于观察到的吲哚分子中的溶剂位移，该位移在整个非线性区域中均已观察到。获得一致的偶极参数，可协调气相和溶液相的结果。

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