title: Theoretical mechanism study of UF6 hydrolysis in the gas phase (II).
abstract: In our previous work (J. Phys. Chem. A 2008, 112, 8877.), we found theoretical evidence indicating UF5OH is an intermediate produced in the first step of UF6 hydrolysis. In this work, we explored the probable reaction channels starting from UF5OH + UF6 and UF5OH + UF5OH systems using relativistic density functional theory calculations. Initially, the two uranium containing species associate to form complex UF6.UF5OH or dimer (UF5OH)2 through hydrogen bonding. The energy released is 12-16 kcal/mol, which may promote further reactions. After H2O or HF are eliminated from the complex or dimer, compounds containing U-O-U bond are produced. These compounds are potentially feasible to associate into larger clusters or solidify. Relative to the isolated initial species, the energies of the final products are -6 to -13 kcal/mol lower, indicating that the reactions may spontaneously proceed. The calculated IR spectra features can be used to indicate the formation and interaction type of the intermediates and products.
authors.affiliation: Beijing National Laboratory of Molecular Sciences (BNLMS), Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing, China 100871. swhu@pku.edu.cn
authors.forename: Shao-Wen
authors.initials: SW
authors.lastname: Hu
authors.forename: Xiang-Yun
authors.initials: XY
authors.lastname: Wang
authors.forename: Tai-Wei
authors.initials: TW
authors.lastname: Chu
authors.forename: Xin-Qi
authors.initials: XQ
authors.lastname: Liu