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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electroabsorption spectra of quadrupolar and octupolar dyes in solution: Beyond the Liptay formulation
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Electroabsorption spectra of quadrupolar and octupolar dyes in solution: Beyond the Liptay formulation

机译：溶液中四极和八极染料的电吸收光谱：超越Liptay配方

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and multipolar (quadrupolar and octupolar) organic chromophores in solutions. Based on essential-state models for the electronic structure, we obtain closed expressions for the EA spectra of these dyes. For polar dyes, we regain the well-known Liptay result, which relates the EA spectrum to the linear absorption spectrum and its first and second derivatives. For multipolar dyes, an additional contribution is found, which is due to the field-induced absorption toward dark states: when the dark states are close in energy to allowed states, this term leads to spurious second-derivative-like structures in the EA spectrum. This is particularly well-apparent for quadrupolar dyes where second-derivative contributions to the EA signal are symmetry-forbidden. The extension of essential-state models to account for slow degrees of freedom, including molecular vibrations and polar solvation, leads to a more-realistic description of optical spectra but hinders the analytical treatment of EA. However, numerically exact EA spectra can be obtained along the same lines that have been recently developed for linear and two-photon absorption spectra of (multi)polar organic chromophores in solution. Essential-state models offer the possibility for a joint analysis of linear and nonlinear spectra (including EA) of (multi)polar dyes: reliable information can then be extracted also on molecular properties for systems where overlapping signals from allowed and dark states would hinder the standard analysis of EA spectra.
机译：和多极（四极和八极）有机发色团。基于电子结构的基本状态模型，我们获得了这些染料的EA光谱的封闭表达式。对于极性染料，我们重新获得了著名的Liptay结果，该结果将EA光谱与线性吸收光谱及其一阶和二阶导数相关。对于多极性染料，发现了额外的贡献，这是由于场诱导的吸收到暗态：当暗态在能量上接近允许态时，该术语会导致EA光谱中出现虚假的类似于二阶导数的结构。这对于四极性染料尤其明显，因为四极性染料对EA信号的二阶导数贡献是对称禁止的。扩展本质状态模型以解决缓慢的自由度，包括分子振动和极性溶剂化，导致对光谱的描述更加真实，但阻碍了EA的分析处理。但是，可以沿与最近为溶液中（多）极性有机发色团的线性和双光子吸收光谱开发的相同谱线获得精确的EA光谱。本质状态模型为（多）极性染料的线性和非线性光谱（包括EA）的联合分析提供了可能性：然后，还可以从系统的分子性质中提取可靠信息，该系统的分子特性来自允许和暗态的重叠信号会阻碍EA光谱的标准分析。

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