在[Cu3S2]3+核心中对可能的S·S相互作用进行X射线吸收光谱和计算研究
Ritimukta Sarangi1, Lei Yang, Stuart G Winikoff
1Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA. ritis@slac.stanford.edu
Journal of the American Chemical Society
|September 20, 2011
概括
这项研究揭示了硫化铜核的电子结构,显示了接近Cu2+氧化和独特的硫物种的铜中心. 这与类似的氧化铜核不同,原因是轨道重叠.
科学领域:
- 无机化学 无机化学
- 材料科学 材料科学 材料科学
- 计算化学的计算化学
背景情况:
- 金属化物核的电子结构对于理解它们的反应性和特性至关重要.
- 之前对类似的氧化铜芯的研究提供了比较的基础.
研究的目的:
- 为了研究 [{LCu}{3}{3}{2}{3}}+) 中的[Cu}{3}{3}{2}}}{3}}+) 核心的电子结构.
- 为了比较电子结构与类似的氧化铜芯.
主要方法:
- Cu 和 S K 边缘X射线吸收光谱学.
- 密度函数理论 (DFT) 的计算.
- 多参照二次扰动理论 (MR-S2PT) 的计算.
主要成果:
- 铜中心在Cu2+附近氧化,硫碎片电荷位于硫化物 (S2-)) 和亚硫化物 (S2-)) 之间.
- [Cu(3) S(2) ](3+) 核心表现出非局部化的电子结构,与类似的[Cu(3) O(2) ](3+) 核心的局部结构不同.
- Cu 3d 和 S 3p 轨道之间的共价重叠增加以及 S 3p 轨道的辐射分布有助于观察到的电子结构.
结论:
- [Cu(3) S(2) ](3+) 核心的电子结构因轨道相互作用的差异而与其氧类同类物有所不同.
- 从S-S σ*轨道到铜的电子密度捐赠稳定了一个移位的S=1基本状态.
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