Kaminský Jakub, Vícha Jan, Bouř Petr, Straka Michal
Institute of Organic Chemistry and Biochemistry AS CR , v.v.i., Flemingovo náměstí 2, 166 10 Prague, Czech Republic.
Center of Polymer Systems, University Institute, Tomáš Bat'a University in Zlín , Třída T. Bati, 5678, CZ-76001, Zlín, Czech Republic.
J Phys Chem A. 2017 Apr 27;121(16):3128-3135. doi: 10.1021/acs.jpca.7b00346. Epub 2017 Apr 13.
Only a single thorium fullerene, Th@C, has been reported to date (Akiyama, K.; et al. J. Nucl. Radiochem. Sci. 2002, 3, 151-154). Although the system was characterized by UV-vis and XANES (X-ray absorption near edge structure) spectra, its structure and properties remain unknown. In this work we used the density functional calculations to identify molecular and electronic structure of the Th@C. Series of molecular structures satisfying the ThC stoichiometric formula were studied comprising 24 IPR and 110 non-IPR Th@C isomers as well as 9 ThC@C IPR isomers. The lowest energy structure is Th@C-C(10) with the singlet ground state. Its predicted electronic absorption spectra are in agreement with the experimentally observed ones. The bonding between the cage and Th was characterized as polar covalent with Th in formal oxidation state IV. The NMR chemical shifts of Th@C-C(10) were predicted to guide the future experimental efforts in identification of this compound.
迄今为止，仅报道了一种钍富勒烯，即Th@C（秋山，K.等人，《核与放射化学科学杂志》，2002年，第3卷，第151 - 154页）。尽管该体系通过紫外可见光谱和X射线吸收近边结构（XANES）进行了表征，但其结构和性质仍不清楚。在这项工作中，我们使用密度泛函计算来确定Th@C的分子结构和电子结构。研究了一系列满足ThC化学计量式的分子结构，包括24种非穿插异构体（IPR）和110种非IPR的Th@C异构体以及9种ThC@C IPR异构体。能量最低的结构是具有单重基态的Th@C - C(10)。其预测的电子吸收光谱与实验观察到的光谱一致。笼与钍之间的键被表征为极性共价键，钍的形式氧化态为IV。预测了Th@C - C(10)的核磁共振化学位移，以指导未来鉴定该化合物的实验工作。
