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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Acid-Base Equilibrium and Electron-Ejection Processes in the Excited States of N,N-Dimethyl-1-aminonaphthalene in Aqueous Solution
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Acid-Base Equilibrium and Electron-Ejection Processes in the Excited States of N,N-Dimethyl-1-aminonaphthalene in Aqueous Solution

机译：N，N-二甲基-1-氨基萘在水溶液中激发态的酸碱平衡和电子喷射过程

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摘要

Acid-base equilibrium and photoinduced electron-ejection processes of N,N-dimethyl-1-aminonaphthalene (DMAN) in aqueous solution have been investigated by nanosecond laser photolysis and fluorescence measurements. Depending on the different pK_a values for the ground (pK_a(S_0) = 4.6), lowest excited singlet (pK_a(S_1) = 2.5), and triplet (pK_a(T_1) = 2.7) states, photoionization pathways varied with acidity of solution. Upon 266 nm laser excitation, the direct electron-ejection took place from the S_1 state of DMAN in aqueous solution at pH > ～6.0, which was revealed to occur from the nonrelaxed S_1 state. At pH 2.0-4.0, proton dissociation took place in the S_1 state of DMANH~+ (protonated DMAN), which was followed by electron-ejection to produce DMAN~(+·). In addition to the above ionization processes, a slow electron-ejection process was found to occur from the T_1 state of DMAN. The possible photoionization mechanisms of aqueous DMAN are discussed on the basis of kinetic analyses, thermochemical considerations, and electronic structures.
机译：通过纳秒激光光解和荧光测量研究了水溶液中N，N-二甲基-1-氨基萘（DMAN）的酸碱平衡和光诱导电子喷射过程。取决于地面的不同pK_a值（pK_a（S_0）= 4.6），最低激发单重态（pK_a（S_1）= 2.5）和三重态（pK_a（T_1）= 2.7）状态，光电离途径随溶液的酸度而变化。在266 nm激光激发下，在pH>〜6.0的水溶液中从DMAN的S_1状态发生直接电子发射，这表明是从非松弛的S_1状态发生的。在pH 2.0-4.0时，质子在DMANH〜+（质子化的DMAN）的S_1状态发生离解，随后进行电子喷射生成DMAN〜（+·）。除了上述电离过程之外，还发现从DMAN的T_1状态开始发生了缓慢的电子喷射过程。在动力学分析，热化学考虑和电子结构的基础上，讨论了水性DMAN可能的光电离机理。

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