UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH2OO),Journal of the American Chemical Society

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UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH2OO)
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-12-24 , DOI: 10.1021/ja510736d
Richard Dawes ₁ , Bin Jiang ₂ , Hua Guo ₂

Affiliation

The lowest-lying singlet states of the simplest Criegee intermediate (CH2OO) have been characterized along the O-O dissociation coordinate using explicitly correlated MRCI-F12 electronic structure theory and large active spaces. It is found that a high-level treatment of dynamic electron-correlation is essential to accurately describe these states. A significant well on the B-state is identified at the MRCI-F12 level with an equilibrium structure that differs substantially from that of the ground X-state. This well is presumably responsible for the apparent vibrational structure in some experimental UV absorption spectra, analogous to the structured Huggins band of the iso-electronic ozone. The B-state potential in the Franck-Condon region is sufficiently accurate that an absorption spectrum calculated with a one-dimensional model agrees remarkably well with experiment.

中文翻译：

最简单的 Criegee 中间体 (CH2OO) 的紫外吸收光谱和光解通道

使用明确相关的 MRCI-F12 电子结构理论和大活性空间，沿着 OO 解离坐标对最简单的 Criegee 中间体 (CH2OO) 的最低单线态进行了表征。发现动态电子相关的高级处理对于准确描述这些状态至关重要。在 MRCI-F12 水平上识别出 B 态的一个重要井，其平衡结构与基态 X 态的平衡结构大不相同。这口井可能是某些实验紫外吸收光谱中明显振动结构的原因，类似于等电子臭氧的结构化哈金斯带。

更新日期：2014-12-24

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