Ca K-edge XAS as a probe of calcium centers in complex systems.
Ca K-edge XAS as a probe of calcium centers in complex systems.
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DOI：
10.1021/ic501991e
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发表时间：
2015-02-16
影响因子：
4.6
通讯作者：
DeBeer S
中科院分区：
文献类型：
--
作者：
Martin-Diaconescu V;Gennari M;Gerey B;Tsui E;Kanady J;Tran R;Pécaut J;Maganas D;Krewald V;Gouré E;Duboc C;Yano J;Agapie T;Collomb MN;DeBeer S
在这里，钙K边X射线吸收光谱（XAS）的开发作为一种手段来表征钙中心的局部环境。六，七，和八个配位无机和分子钙配合物的光谱进行了分析，并确定主要是受钙中心的配位环境和站点对称性的影响。实验结果与含时密度泛函理论（TD-DFT）计算的XAS光谱密切相关。这种方法的复杂系统的适用性进行了研究，使用结构模拟的氧气演变复杂（OEC）的PSII。结果发现，钙K边XAS是一个敏感的探针的结构变化发生在立方烷异金属簇由于锰氧化。OEC的未来应用进行了讨论。钙离子K边预边结合TD-DFT理论计算为无机和生物无机化学中复杂钙离子中心的表征提供了一种强有力的方法。
Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed. Calcium K-edge pre-edges coupled with TD-DFT theoretical calculation of spectra provide a powerful approach for the characterization of complex calcium centers in inorganic and bioinorganic chemistry.
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影响因子：
1.7
作者：
BERGNER, A;DOLG, M;PREUSS, H
通讯作者：
PREUSS, H
影响因子：
4.3
作者：
Atkins, Andrew J.;Jacob, Christoph R.;Bauer, Matthias
通讯作者：
Bauer, Matthias
影响因子：
4.4
作者：
Bernadotte, Stephan;Atkins, Andrew J.;Jacob, Christoph R.
通讯作者：
Jacob, Christoph R.
影响因子：
3.9
作者：
Cormier, L;Neuville, DR
通讯作者：
Neuville, DR
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD