Ultrafast Dynamics of Bimolecular Reactions in Solution

溶液中双分子反应的超快动力学

• 批准号: 267090720
• 负责人: Dr. Katharina Röttger
• 金额: --
• 依托单位: Institut für Physikalische Chemie
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/267090720?language=en
• 关键词: Ultrafast; Dynamics; Bimolecular; Reactions; Solution

The investigation of bimolecular reaction dynamics in solution provides a means of understanding the fundamental aspects and elementary steps that are important in numerous chemical reactions, among them nucleophilic substitution, elimination and addition reactions, and many catalysed reactions. In this project, the influence of hydrogen bonding and complexation on the potential energy landscape of bimolecular reactions in the liquid phase will be investigated. Hydrogen bonds are particularly important in, e.g., enzyme catalysed reactions, where the transition state is characterized by a large number of hydrogen bonds and H-transfer reactions. A detailed understanding of their role is, however, still missing. For this reason, reactions with less complexity, which are expected to shed light on the very basic steps of these reactions, will be investigated in this project. The first part covers the reactions of CN radicals with small reaction partners. The use of co-reactants and solvents with different H-bonding properties is expected to elucidate the role of surrounding solvent molecules on the potential energy landscape by complexation and/or proton transfer reactions. The reactivity of CN and OH radicals in and with water will be investigated in the second part of this project. These reactions will provide direct insight into the role of ubiquitous hydrogen bonds. A combination of femtosecond time-resolved transient IR and UV/vis spectroscopy will be used to look into the formation of the involved complexes, the making and breaking of H-bonds, the rates of product formation and vibrational relaxation mechanisms in real time.

溶液中双分子反应动力学的研究提供了一种理解许多化学反应中重要的基本方面和基本步骤的方法，其中包括亲核取代，消除和加成反应以及许多催化反应。在这个项目中，氢键和络合作用对液相中双分子反应势能景观的影响将被研究。氢键是特别重要的，例如，酶催化反应，其中过渡态的特征在于大量的氢键和H-转移反应。然而，对他们的作用仍然缺乏详细的了解。因此，本项目将研究复杂性较低的反应，这些反应有望揭示这些反应的最基本步骤。第一部分包括CN自由基与小反应伙伴的反应。使用具有不同氢键性质的共反应物和溶剂有望通过络合和/或质子转移反应阐明周围溶剂分子对势能景观的作用。CN和OH自由基在水中和与水的反应性将在本项目的第二部分进行研究。这些反应将提供对无处不在的氢键的作用的直接洞察。飞秒时间分辨瞬态红外光谱和紫外/维斯光谱的组合将被用来研究所涉及的复合物的形成，氢键的形成和断裂，产品形成的速率和振动弛豫机制在真实的时间。