摄影化学路径到八面体铁(V). 从超快中红外光谱学中获得的初级过程和量子产量
Hendrik Vennekate1, Dirk Schwarzer, Joel Torres-Alacan
1Max-Planck-Institut für biophysikalische Chemie , Am Fassberg 11, 37077 Göttingen, Germany.
Journal of the American Chemical Society
|June 21, 2014
概括
光化学研究表明,紫外线光,而不是可见光,产生高价值铁化物从溶液中的[-ac) Fe (III) (N3) ] (N+). 光氧化与光还原和键断裂在五秒钟内竞争.
科学领域:
- 摄影化学的使用.
- 无机化学 无机化学
- 频谱学是一种光谱学.
背景情况:
- 复杂的阳离子[-ac]Fe[III][N3][+]是一种已知的光化学前体.
- 之前的研究在冷条件下使用了固体矩阵.
研究的目的:
- 研究室温液溶液中复杂的光化学初级事件.
- 将溶液的行为与之前的冷矩阵实验进行比较.
主要方法:
- 五秒钟时间分辨率的中红外光谱 (fs-MIR).
- 步骤扫描里埃变换红外光谱学.
- 可变波长激发. 波长变化的激发.
主要成果:
- 可见光激发 (LMCT带) 导致氧化-中性亚解离,而不是光氧化.
- 紫外线激发形成高价值铁化物产物.
- 光氧化与光还原Fe-N键裂和N-N键断裂在五秒钟内竞争.
- 双胞胎重组发生在皮秒时间尺度上.
结论:
- 溶液光化学与冷矩阵结果有很大的不同.
- 紫外线光解对于产生高价值铁化物是有效的,但需要仔细考虑竞争的途径.
- 光氧化的主要量子产量随着光子能量的增加而增加.
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