Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

• Published in: Chemphyschem 2023-04, Vol.24 (7), p.e202200701-n/a
• Main Authors: Wang, Bin, Ye, Shu, Zhang, Si‐Yuan, Fang, Hong‐Ling, Zhang, Yong‐Fan, Xia, Chan‐Juan, Chen, Wen‐Jie
• Format: Article
• Language: English
• Subjects: chemical bonding; Clusters; Hydrolysis; Industrial applications; Oxygen; Oxygen content; reaction mechanism; Reaction mechanisms; Thorium; thorium oxide cluster; Thorium oxides
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.202200701

Thorium oxide has many important applications in industry. In this article, theoretical calculations have been carried out to explore the hydrolysis reactions of the ThOn (n=1–3) clusters. The reaction mechanisms of the O‐deficient ThO and the O‐rich ThO3 are compared with the stoichiometric ThO2. The theoretical results show good agreement with the prior experiments. It is shown that the hydrolysis mainly occurred on the singlet potential surface. The overall reactions consist of two hydrolysis steps which are all favourable in energy. The effects of oxygen content on the hydrolysis are elucidated. Interestingly, among them, the peroxo group O22− in ThO3 is converted to the HOO− ligand, behaving like the terminal O2− in the hydrolysis which is transformed into the HO− groups. In addition, natural bond orbital (NBO) analyses were employed to further understand the bonding of the pertinent species and to interpret the differences in hydrolysis. The hydrolysis mechanisms of ThO and ThO3 are compared with that of ThO2. All of them can be divided into two hydrolysis steps, which are all favourable in energy. However, there are some differences in the reaction mechanisms; the reasons for these differences are discussed.