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利用飞秒受激拉曼光谱研究9-(2,2-二氰乙烯基)久洛啶中分子内扭转电荷转移和异构化动力
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作者 王正心 姜甲明 +1 位作者 黄逸凡 刘伟民 《Chinese Journal of Chemical Physics》 SCIE EI CAS CSCD 2023年第4期397-403,I0034,共8页
本文利用飞秒受激拉曼光谱结合量子化学计算研究了9-(2,2-二氰乙烯基)久洛啶分子在环已烷、四氢呋喃和二甲基亚砜溶剂中的激发态结构动力学.实验中观测到该分子的氢原子离面振动模式以及双基(C=N)对称/反对称伸缩振动模式,这两种振动模... 本文利用飞秒受激拉曼光谱结合量子化学计算研究了9-(2,2-二氰乙烯基)久洛啶分子在环已烷、四氢呋喃和二甲基亚砜溶剂中的激发态结构动力学.实验中观测到该分子的氢原子离面振动模式以及双基(C=N)对称/反对称伸缩振动模式,这两种振动模式的发现意味着该分子在光激发后将沿C7=Cg双键和C4-C7单键进行扭转,即通过异构化和分子内扭转电荷转移两种无辐射弛豫方式有效地淬灭局域性激发态上的粒子数.在非极性溶剂中,光激发导致局域性激发态的粒子数布居,其中一部分粒子数通过异构化以无辐射形式弛豫回基态;此外,虽然非极性溶剂中没有出现分子内电荷传中间态,部分局域性激发态粒子数直接通过荧光发射弛豫回到基态,另一部分局域性激发态粒子数则通过分子内扭转电荷转移过程无辐射弛豫回基态.在极性溶剂中,光激发导致局域性激发态粒子数布居,其中一部分粒子数通过异构化无辐射弛豫回基态;另一部分局域性激发态的粒子数通过超快的分子内电荷传递过程弛豫至分子内电荷传递发光态,分子内电荷传递态上的粒子数一部分通过荧光发射弛豫回到基态,另一部分则通过分子内扭转电荷转移过程以无辐射形式弛豫到分子内电荷传递暗态。 展开更多
关键词 飞秒受激拉曼光谱 分子内扭转电荷转移 异构化 氢原子离面振动模式
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Observation of Refractive Index Line Shape in Ultrafast XUV Transient Absorption Spectroscopy 被引量:3
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作者 Mingze Sun Zixiang jiang +11 位作者 Yong Fu Yanrong jiang Hongtao Hu Chunyuan Bai Zhongyao Yue jiaming jiang Hongqiang Xie Cheng Jin Ruxin Li P.B.Corkum D.M.Vileneuvere Ppeng Peng 《Ultrafast Science》 2023年第4期25-34,共10页
Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light ... Ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy measures the time- and frequencydependent light losses after light–matter interactions. In the linear region, the matter response to an XUV light field is usually determined by the complex refractive index ̃n. The absorption signal is directly related to the imaginary part of ̃n, namely, the absorption index. The real part of ̃n refers to the real refractive index, which describes the chromatic dispersion of an optical material. However, the real refractive index information is usually not available in conventional absorption experiments. Here, we investigate the refractive index line shape in ultrafast XUV transient absorption spectroscopy by using a scheme that the XUV pulse traverses the target gas jet off-center. The jet has a density gradient in the direction perpendicular to the gas injection direction, which induces deflection on the XUV radiation. Our experimental and theoretical results show that the shape of the frequency-dependent XUV deflection spectra reproduces the refractive index line profile. A typical dispersive refractive index line shape is measured for a single-peak absorption;an additional shoulder structure appears for a doublet absorption.Moreover, the refractive index line shape is controlled by introducing a later-arrived near-infrared pulse to modify the phase of the XUV free induction decay, resulting in different XUV deflection spectra. The results promote our understanding of matter-induced absorption and deflection in ultrafast XUV spectroscopy. 展开更多
关键词 Attosecond transient absorption spectroscopy line shape refractive index High Harmonic Generation
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