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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theory of the Salt Effect on Solvatochromic Shifts And Its Potential Application to the Determination of Ground-State and Excited-State Dipole Moments
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Theory of the Salt Effect on Solvatochromic Shifts And Its Potential Application to the Determination of Ground-State and Excited-State Dipole Moments

机译：盐对溶剂变色位移的影响理论及其在测定基态和激发态偶极矩中的潜在应用

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摘要

The theory of solvatochromism based on a dielectric continuum description of the solvent and the classical Onsager cavity model is revisited and extended to include the effect of an added 1:1, salt. An expression is derived fro the reaction field inside the solute cavity, which is applicable in the limit of low salt concentrations. Using this result, expressions are obtained for the shifts in the (0-0) absorption and fluorescence maxima on the basis of Marcus' approach to the calculation of the medium reorganization free energy in the ground state and excited (Franck-Condon) state of the solute molecule. The lifetime of the excited state is assumed to exceed the longest relaxation time characteristic of the medium. For the salt-free case, our equations differ markedly from several others reported in the literature dealing with the pure solvent effect, and the origin of the discrepancy is clarified. Finally, it is shown how the new equations can be used, in principle, to obtain estimates for the Onsager radius, polarizability, and dipole moments in the ground state and the lowest excited state of a solute molecule from a simple analysis of absorption and fluorescence data only, except in cases where the dipole moments are noncollinear. Completion of the analysis then requires an independent measurement of the ground-state dipole moment.
机译：重新研究了基于溶剂的介电连续性描述和经典Onsager腔模型的溶剂变色理论，并将其扩展为包括添加1：1盐的作用。由溶质腔内部的反应场得出一个表达式，该表达式适用于低盐浓度的限制。利用该结果，基于Marcus方法计算基态和激发态（Franck-Condon）的介质重组自由能，获得了（0-0）吸收和荧光最大值的位移表达式。溶质分子。假定激发态的寿命超过介质的最长弛豫时间特性。对于无盐的情况，我们的方程与文献中有关纯溶剂效应的其他方程式明显不同，并且澄清了差异的来源。最后，说明了如何从原理上通过简单的吸收和荧光分析，可以使用新的方程式估算溶质分子在基态和最低激发态下的昂萨格半径，极化率和偶极矩偶极矩不共线的情况除外。然后，要完成分析，需要对基态偶极矩进行独立测量。

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