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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >NH Stretching Vibrations of Jet-Cooled Aniline and Its Derivatives in the Neutral and Cationic Ground States
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NH Stretching Vibrations of Jet-Cooled Aniline and Its Derivatives in the Neutral and Cationic Ground States

机译：中性和阳离子基态下喷射冷却苯胺及其衍生物的NH伸缩振动

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摘要

NH stretching vibrations of jet-cooled aniline and its various derivatives were observed in the neutral and cationic ground states. Infrared-ultraviolet double-resonance spectroscopy was utilized for the observation in the neutral ground state, and autoionization-detected infrared spectroscopy was used in the measurement of the cationic ground state. Low-frequency shifts of the NH frequencies were seen upon ionization, though the magnitude of the shifts was much smaller than those of the OH stretching vibrations observed for phenol derivatives. NH vibrational frequencies of meta and para isomers of aniline derivatives showed a positive correlation with the Hammett σ parameters of the substituents in the neutral ground state, while a negative correlation was found for the cationic ground state. Intramolecular hydrogen bond formation was found for o-cyanoaniline in both the neutral and cationic ground states based on the infrared spectra of deuterated isotopomers as well as theoretical calculations, showing that the hydrogen bond strength is remarkably enhanced upon ionization.
机译：在中性和阳离子基态下观察到喷射冷却的苯胺及其各种衍生物的NH伸缩振动。红外-紫外双共振光谱法用于中性基态的观察，而自电离检测的红外光谱法用于阳离子基态的测量。电离时可以看到NH频率的低频位移，尽管该位移的幅度比苯酚衍生物的OH拉伸振动小得多。苯胺衍生物间位和对位异构体的NH振动频率与中性基态取代基的Hammettσ参数呈正相关，而与阳离子基态呈负相关。根据氘化的同位素异构体的红外光谱和理论计算，发现了中性和阳离子基态的邻氰基苯胺分子内氢键形成，表明电离后氢键强度显着提高。

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