Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers
Chemical interactions and dynamics with femtosecond X-ray spectroscopy and the role of X-ray free-electron lasers
复制标题
飞秒 X 射线光谱的化学相互作用和动力学以及 X 射线自由电子激光器的作用
DOI：
10.1098/rsta.2017.0464
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
P. Wernet
中科院分区：
文献类型：
--
作者：
P. Wernet
X射线自由电子激光器具有强、可调和短脉冲X射线辐射，是研究过渡金属络合物和金属蛋白质的变革性工具。当将X射线光谱学的实验观测值与用于计算电子结构和X射线光谱的第一原理的现代理论工具相结合时，这一点尤其明显。这一组合为化学反应中电荷和自旋密度的变化以及它们如何决定反应性提供了新的见解。这是证明了与金属K边吸收光谱，自旋态的激发态动力学与金属3 p-3d交换相互作用，在解离和取代反应与金属特定的X-射线光谱的前沿轨道相互作用的结构动力学的调查，和金属氧化态的研究与飞秒脉冲的“探测前破坏”光谱。X射线自由电子激光器的作用是解决与思考他们如何使“带回一起”同一问题的不同方面，这被认为是超越了传统的审查文件，这些方面是制定在斜体字体类型的前传，插曲和续集。这篇文章是“用X射线测量超快电子和结构动力学”主题的一部分。
X-ray free-electron lasers with intense, tuneable and short-pulse X-ray radiation are transformative tools for the investigation of transition-metal complexes and metalloproteins. This becomes apparent in particular when combining the experimental observables from X-ray spectroscopy with modern theoretical tools for calculations of electronic structures and X-ray spectra from first principles. The combination gives new insights into how charge and spin densities change in chemical reactions and how they determine reactivity. This is demonstrated for the investigations of structural dynamics with metal K-edge absorption spectroscopy, spin states in excited-state dynamics with metal 3p-3d exchange interactions, the frontier-orbital interactions in dissociation and substitution reactions with metal-specific X-ray spectroscopy, and studies of metal oxidation states with femtosecond pulses for ‘probe-before-destroy’ spectroscopy. The role of X-ray free-electron lasers is addressed with thoughts about how they enable ‘bringing back together’ different aspects of the same problem and this is thought to go beyond a conventional review paper where these aspects are formulated in italic font type in a prequel, an interlude and in a sequel. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays'.