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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structure and Dynamics of the Solvated Electron in Alcohols from Resonance Raman Spectroscopy
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Structure and Dynamics of the Solvated Electron in Alcohols from Resonance Raman Spectroscopy

机译：共振拉曼光谱法研究醇中溶剂化电子的结构和动力学

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摘要

Resonance Raman(RR)spectroscopy is used to probe the structure and excited-state dynamics of the solvated electron in the primary liquid alcohols methanol(MeOH),ethanol(EtOH),n-propanol(n-PrOH),and n-butanol(n-BuOH).The strong resonance enhancements(>=10~4 relative to pure solvent)of the libration,CO stretch,COH bend,CH3 bend,CH2 bend,and OH stretch reveal significant Franck-Condon coupling of the intermolecular and intramolecular vibrational modes of the solvent to the electronic excitation of the solvated electron.All enhanced bands are fully accounted for by a model of the solvated electron that is comprised of several nearby solvent molecules that are only perturbed by the presence of the electron;no new molecular species are required to explain our data.The 340 cm~(-1)downshift observed for the OH stretch frequency of e~-(MeOH),relative to pure solvent,strongly suggests that the methanol molecules in the first solvent shell have the hydroxyl group directed linearly toward the excess electron density.The smaller downshifts observed for e~-(EtOH),e~-(n-PrOH),and e~-(n-BuOH)are explained in terms of a OH group that is bent 28-40 deg from linear.The Raman cross sections and absorption spectra are modeled,lending quantitative support for the inhomogeneous origin of the broad absorption spectra,the necessity of OH local motion in all enhanced Raman modes of the alcohols,and the dominant librational response of the solvent upon photoexcitation of the electron.
机译：共振拉曼光谱（RR）用于探测主要液态醇甲醇（MeOH），乙醇（EtOH），正丙醇（n-PrOH）和正丁醇（正丁醇）中溶剂化电子的结构和激发态动力学释放，CO拉伸，COH弯曲，CH3弯曲，CH2弯曲，OH拉伸的强烈共振增强（相对于纯溶剂为> 10〜4）显示出分子间和分子内的明显Franck-Condon偶联溶剂的振动模式对溶剂化电子的电子激发。所有增强谱带均由溶剂化电子模型完全解释，该模型由几个附近的溶剂分子组成，仅受电子的存在干扰;没有新分子需要使用物种来解释我们的数据。相对于纯溶剂，e〜-（MeOH）的OH拉伸频率观察到的340 cm〜（-1）下移，强烈表明第一溶剂壳中的甲醇分子具有羟基线性指向发泄的组ss电子密度对拉曼横截面和吸收光谱进行建模，为宽吸收光谱的不均匀起源，在所有增强的拉曼醇模式中OH局部运动的必要性以及光激发时溶剂的主要自由反应提供了定量支持电子。

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