Spectroscopy of the breaking bond: the diradical intermediate of the ring opening in oxazole.
Spectroscopy of the breaking bond: the diradical intermediate of the ring opening in oxazole.
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断键光谱：恶唑开环的双自由基中间体。
DOI：
10.1039/c3cp54779e
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
A. Sanov
中科院分区：
文献类型：
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作者：
L. M. Culberson;A. A. Wallace;Christopher C. Blackstone;Dmitry Khuseynov;A. Sanov
由于解离分子的瞬态性质和多构型电子结构，断键在实验和理论化学中都是一个具有挑战性的问题。我们利用阴离子的光剥离来探测恶唑开环反应中的双自由基相互作用，并获得了自洽的断键图。从闭壳环分子开始，反应是在阴离子电位上启动的，因为一个附着的电子分裂了碳-氧键。在光分离中，对两个中性电位区进行采样。一个对应于完全解离的键，而另一个-对应于大约3的键片段Å。在这个化学上相关的距离上，可以观察到自由基中心之间在空间中相互作用的特征。
Bond breaking is a challenging problem in both experimental and theoretical chemistry, due to the transient nature and multi-configurational electronic structure of dissociating molecules. We use anion photodetachment to probe the diradical interactions in the ring-opening reaction of oxazole and obtain a self-consistent picture of the breaking bond. Starting from the closed-shell cyclic molecule, the reaction is launched on the anion potential, as an attached electron cleaves a carbon-oxygen bond. In the photodetachment, two neutral potential regions are sampled. One corresponds to a completely dissociated bond, while the other - to the bond fragments separated by approximately 3 Å. At this chemically relevant distance, signatures of lingering through-space interactions between the radical centers are observed.