Leszczyk Aleksandra, Dome Tibor, Tecmer Paweł, Kedziera Dariusz, Boguslawski Katharina
Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University in Toruń, Grudziadzka 5, 87-100 Toruń, Poland.
Institute for Theoretical Physics, ETH Zürich, 8093 Zürich, Switzerland.
Phys Chem Chem Phys. 2022 Sep 14;24(35):21296-21307. doi: 10.1039/d2cp03377a.
We model the potential energy profiles of the UO (NCO)Cl → NUOCl + CO reaction pathway [Y. Gong, V. Vallet, M. del Carmen Michelini, D. Rios and J. K. Gibson, , 2014, , 325-330] using different pair coupled-cluster doubles (pCCD) methods. Specifically, we focus on pCCD and pCCD-tailored coupled cluster models in predicting relative energies for the various intermediates and transition states along the reaction coordinate. Furthermore, we augment our study on energetics with an orbital-pair correlation analysis of the complete reaction pathway that features two distinct paths. Our analysis of orbital correlations sheds new light on the formation and breaking of respective bonds between the uranium, oxygen, and nitrogen atoms along the reaction coordinates where the "yl" bond is broken and a nitrido compound formed. Specifically, the strengthening of the U-N σ-bond is assisted by a π-type interaction that is delocalized over the C-N-U backbone of the UO (NCO)Cl complex.
我们使用不同的对耦合簇双激发（pCCD）方法，对UO (NCO)Cl → NUOCl + CO反应路径的势能面进行了建模[Y. Gong, V. Vallet, M. del Carmen Michelini, D. Rios和J. K. Gibson, ，2014, ，325 - 330]。具体而言，我们重点关注pCCD和pCCD定制的耦合簇模型，以预测沿反应坐标的各种中间体和过渡态的相对能量。此外，我们通过对具有两条不同路径的完整反应路径进行轨道对相关分析，来扩充我们对能量学的研究。我们的轨道相关分析为沿着反应坐标的铀、氧和氮原子之间各自化学键的形成和断裂提供了新的见解，在该反应坐标中，“yl”键断裂并形成了氮化物化合物。具体来说，U-N σ键的强化是由一种π型相互作用辅助的，这种相互作用在UO (NCO)Cl络合物的C-N-U主链上离域。
