Dynamics of Gas-Phase Clusters as Studied by Tune-Resolved Photoelectron

调谐分辨光电子研究气相团簇动力学

• 批准号: 09440210
• 负责人: NAGATA Takashi
• 金额: $ 7.49万
• 依托单位: The University of Tokyo (1998-1999)Okazaki National Research Institutes (1997)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440210/
• 关键词: Molecular cluster anions; Photoelectron spectroscopy; Energy dissipation; Electronic isomer; Structural fluctuation; Tri-iodide anion; Solvent effects; Microsolvation

One of the fundamental issues regarding the properties of clusters, aggregates of atoms or molecules in the gas phase, concerns the dynamics of energy dissipation among their enormous numbers of degrees of freedom. In the present study, we have investigated (1) the energy relaxation processes, (2) the isomerization processes and (3) photodissociation processes of negatively-charged molecular clusters in terms of their geometrical and electronic structures. The findings are summarized as follows :1. The time evolution of the photoelectron signal from an electronically-excited (CィイD26ィエD2FィイD26ィエD2)ィイD2nィエD2ィイD1-ィエD1 is probed by fs time-resolved photoelectron spectroscopy. The excited state is found to decay with a lifetime of 1.5 ps, which can be regarded as the time required for the energy disposal into a specific intermolecular vibrational mode in the cluster anions.2. The electronic structures of (C0ィイD22ィエD2)ィイD2nィエD2ィイD1-ィエD1, (CSィイD22ィエD2)ィイD2nィエD2ィイD1-ィエD1 and [(C0ィイD22ィエD2)ィイD2 … More nィエD2ROH]ィイD1-ィエD1 (R = H, CHィイD23ィエD2) are investigated by photoelectron spectroscopy combined with ab initio calculations, demonstrating the coexistence of isomers having different electronic structures. These "electronic isomers" are well described as [CィイD22ィエD2OィイD24ィエD2ィイD1-ィエD1・ROH(COィイD22ィエD2)ィイD2n-2ィエD2] and [C0ィイD22ィエD2ィイD1-ィエD1・ROH (COィイD22ィエD2)ィイD2n-1ィエD2]3. The photodepletion-photoelectron measurement has revealed the floppiness of the isomeric forms of [(C0ィイD22ィエD2) ィイD24ィエD2HィイD22ィエD2O]ィイD1-ィエD1 clusters : the cluster anions are fluctuating between two forms of isomers as [CィイD22ィエD2OィイD24ィエD2ィイD1-ィエD1・HィイD22ィエD2O (C0ィイD22ィエD2) ィイD22ィエD2] 【double arrow】 [C0ィイD22ィエD2ィイD1-ィエD1・HィイD22ィエD20(C0ィイD22ィエD2) ィイD23ィエD2] at their own temperatures.4. The photodissociation processes of gas-phase tri-iodide anion, IィイD23ィエD2ィイD1-ィエD1, along with its weakly bound clusters, IィイD23ィエD2ィイD1-ィエD1・M, are studied by a combination of an ion-beam technique with a time-of-flight (TOF) method. The experimental results obtained shows convincingly that a single solvent molecule can inhibit the more energy-demanding channel of the IィイD23ィエD2ィイD1-ィエD1 photofragmentation to a considerable extent, which opens up a possibility of controlling the IィイD23ィエD2ィイD1-ィエD1 photofragmentation process via stepwise microsolvation. Less

关于气相中簇，原子骨料或分子骨料的性质的基本问题之一，涉及其增强的自由度数量之间的能量耗散的动力学。在本研究中，我们已经研究了（1）能量弛豫过程，（2）异构化过程和（3）根据其几何和电子结构的否定分子簇的光解离过程。调查结果总结如下：1。来自电子激发（CII D26，D26，D2）CII D2N，D2，D1-D1的光电信号的时间演变由FS时间分辨的光电学光谱探测。发现激发态的寿命为1.5 ps，可以将其视为能量处理所需的时间，以在簇阴离子中的特定分子间振动模式中。2。 （C0D22E D2）II D2NE D2NE D1-E D1，（CSD22E D2）II D2NE D2…更多NIE D2ROH] II D1-E D1（R = H，CHD23E D2）的电子结构与Electio ISOM相同，该II d1-e d2ne II D2Ne D2…II D1-E D1 D1（R = H，CHD23E D2）与Electio ISOM相结合，与Excipopy相同，该构建构成了coex insornitions coexsistions coexsisiss insom in coexsisiss。这些“电子异构体”很好地描述为[C0D22E D2OI D24E D2II D1-E D1 d1 roH（COI D22E D2）II D2N-2E D2]和[C0D22E D2-ED2-E D1-E D1-E D1-D1-D1-D1-D1 D1 roH（COI D22E D2 D2 D2）II D2N-1E D2] 3。已经揭示了[（C0D22E D2）II D24E D22HE D22E D22O D2O] II D1-E D1簇的异构形式的磷的光播 - 电电测量：群集群在两种形式之间波动[C0D22E D2）II D24E D22E D22E D22O D22O] II D1-E D1簇。 D22E D2O（C0D22E D2）D22E D2] [Double Arrow] [C0D22E D2I D1-E D1-E D1 d1 hi D22E D20（C0D22E D2）D2）D2 D2]在他们自己的温度下。4。气相三碘阴离子的光解离过程I D23E D2I D1-E D1及其弱结合的簇I D23E D2I D1-E D1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1 d1-e d1-e d1-e d1-e d1-e d1-e d1-e d1 d1-e d1 d1-e d1 d1-e d1 d1-e。获得的实验结果令人信服地表明，单个溶剂分子可以抑制II D23 D2I D1-I D1 D1 PhotoFofragpertation的更为能量的通道，从而开放了控制II D23 D2I D2I D1-I D1-I D1 PhotoFofigagragation Photofragation Procession逐步通过逐步进行逐步进行的微化处理的可能性。较少的

项目成果

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