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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ultrafast Reactivity of IR-Excited Electron in Aqueous Ionic Solutions
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Ultrafast Reactivity of IR-Excited Electron in Aqueous Ionic Solutions

机译：离子水溶液中红外激发电子的超快反应性

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An ultrafast presolvation reaction involving IR-excited hydrated electrons and bivalent metal cations (Cd↑(2+))↓(aq) was investigated at the femtosecond time scale. The initial electron photodetachment is triggered by a two-photon UV excitation of aqueous chloride ions (R = [H↓(2)O]/[XCl↓(2)] = 110). The photodetached electron reaches a IR p-like state (prehydrated electron) with a time constant of 130 fs at 294 K. In the presence of nonreactive divalent alkaline metal cations (X↑(2+) = Mg250L?2+)), this transient IR electronic state exhibits a deactivation process toward the ground state of hydrated electron (s state) with a time constant of 300 ± 20 fs. In aqueous CdCl↓(2) solution, an ultrafast IR electron transfer channel (univalent reduction of Cd↑(2+) by IR prehydrated electrons) competes with the p → s transition of trapped electrons (electron solvation process). This presolvation reaction occurs with a characteristic time of 140 ± 20 fs. Within the electron solvation regime, this elementary redox process is totally achieved in less than 1 × 10↑(-12) s and exhibits a probability 10 times higher than the electron hydration channel. The consequence of an early partition between reactive and nonreactive IR electron dynamics on the subpicosecond formation of fully hydrated electron is discussed. The femtosecond IR spectroscopy of excited p-state electron transfer processes in aqueous electrolyte solutions opens a new area of prethermal reactions in environments relevant to mainstream chemistry and biochemistry.
机译：在飞秒时间内研究了涉及IR激发的水合电子和二价金属阳离子（Cd↑（2 +））↓（aq）的超快预溶剂化反应。最初的电子光解离是由氯离子的双光子UV激发触发的（R = [H↓（2）O] / [XCl↓（2）] = 110）。光解离电子在294 K时达到IR f样状态（预水合电子），时间常数为130 fs。在存在非反应性二价碱金属阳离子的情况下（X↑（2+）=Mg250L？2+） ，该瞬态IR电子态以300±20 fs的时间常数向水合电子的基态（s态）表现出失活过程。在CdCl↓（2）水溶液中，超快的IR电子传输通道（通过IR预水合电子单价还原Cd↑（2+））与捕获电子的p→s跃迁竞争（电子溶剂化过程）。该预溶剂化反应的特征时间为140±20 fs。在电子溶剂化范围内，该基本氧化还原过程完全在不到1×10↑（-12）s内完成，并且其概率比电子水化通道高10倍。讨论了反应性和非反应性IR电子动力学之间的早期分配对亚皮秒级完全水合电子形成的影响。飞秒红外光谱在电解质水溶液中激发p状态电子转移过程的过程中，在与主流化学和生物化学有关的环境中开启了预热反应的新领域。

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