Cooperation Research Unit

跨学科研究小组FOR1405将物理学家和化学家的努力集中在利用尖端光子源进行与催化和酶反应相关的生物无机铜模型系统中的电荷转移过程领域的专门研究。该方法结合了先进的生物无机铜化学和复杂的光谱学，利用了脉冲激光、自由电子激光和第三代同步加速器应用的巨大潜力。在最雄心勃勃的层面上——for是最重要的先决条件——它为我们提供了关于电荷转移动力学的基本见解，其时间分辨率在飞秒到纳秒之间，与生物无机化学有很大的相关性。使用软、硬x射线自由电子激光器与高端同步加速器源（如PETRA III）相结合的技术基础是通过使用高端实验室激光源来实施和验证新的实验技术（如现代喷气技术）的补充。因此，全范围的现代拉曼光谱（共振和泵浦探针拉曼）以及x射线吸收光谱（XAS， HERFD， XES，泵浦探针XAS）被应用于整个过程。电荷转移包括多个基本步骤：首先，电子从金属移到配体上（内球过程），导致电荷在小距离上分离。在下一步中，这个电子可以在外球过程中转移到外部氧化剂上。随后，电子在更远的距离上转移到其他氧化还原伙伴（电荷传输）。在第一个融资期，我们专注于酪氨酸酶和CuA模型。为了更深入地研究潜在的球内电子转移过程，我们选择通过研究单核铜配合物作为零型铜蛋白的模型来补充双核和多核模型配合物的研究。所有三种类型的模型都允许在受控环境中研究电子转移的具体问题，每个子项目都侧重于两种基本的电荷/电子转移现象。我们将利用激发态动力学方面的知识，对所涉及的电荷转移动力学进行详细的微观和量子力学理解。在计算方面，计划在第二个资助期发展方法和理论光谱学。为了更真实地描述分子电子结构，我们将把研究扩展到包括非共线自旋极化在内的全相对论性计算。结合破对称计算，我们特别希望探索和合理化迪铜配合物的自旋结构。

The interdisciplinary research group FOR1405 focuses the efforts of physicists and chemists to utilize cutting edge photon sources for the dedicated research in the area of charge transfer processes in bioinorganic copper model systems that are relevant for catalytic and enzymatic reactions.The concerted approach merges advanced bioinorganic copper chemistry and sophisticated spectroscopy that makes use of the tremendous potential of pulsed laser, free-electron laser and 3rd-generation-synchrotron applications. At its most ambitious level - for which the FOR is the most important prerequisite -, it provides us with fundamental insights into charge transfer dynamics with a time resolution between femtoseconds to nanoseconds with large relevance for bioinorganic chemistry.The technical foundation for the use of soft and hard X-ray free-electron lasers in connection with high-end synchrotron sources such as PETRA III is complemented by the use of high-end lab-based laser sources to implement and validate new experimental techniques such as modern jet technologies. The full range of modern Raman spectroscopy (resonance and pump-probe Raman) as well as of X-ray absorption spectroscopy (XAS, HERFD, XES, pump-probe XAS) is herefore applied throughout.Charge transfer comprises multiple elementary steps: Firstly, an electron is removed from the metal to a ligand (inner-sphere process) leading to a charge separation over small distances. In a next step this electron can be transferred to an external oxidant during an outer-sphere process. Subsequently, the electron is transferred over longer distances to other redox partners (charge transport).In the first funding period, we focused on Tyrosinase and CuA models. In order to investigate more thoroughly the underlying inner-sphere electron transfer processes, we chose to complement these studies on bi- and polynuclear model complexes by studying mononuclear copper complexes as models for Type Zero copper proteins. All three types of models allow for investigating specific questions on electron transfer in a controlled environment with each subproject focusing on two basic charge/electron transfer phenomena. We will use our knowledge on the dynamics of the excited state to allow a detailed microscopic and quantum mechanical understanding of the involved charge transfer dynamics. On the computational side, methodological developments as well as theoretical spectroscopy are planned for the second funding period. In order to achieve a more realistic description of the molecular electronic structure we will extend our studies towards full relativistic calculations including non-collinear spin polarization. In conjunction with broken symmetry calculations we hope in particular to explore and rationalize the spin structure of the dicopper complexes.