Energetic and Electronic Properties of UO^0/± and UF^0/±

Abstract

High-level electronic structure calculations were conducted to examine the bonding and spectroscopic properties of the UO 0/± and UF 0/± diatomic molecules. The low-lying Ω states were described by using multireference SO-CASPT2 calculations. The adiabatic electronic affinity (AEA), adiabatic ionization energy (IE), and bond dissociation energy (BDE) were calculated at the Feller−Peterson−Dixon (FPD) level. The ground state of UO is predicted to be 5 I 4 , and that of UF is 4 I 9/2 . The calculated AEAs of UO and UF are 1.123 and 0.453 eV, respectively, and the corresponding IEs are 5.976 and 6.278 eV. The BDE of UO (749.5 kJ/mol) is predicted to be considerably higher than that of UF (627.2 kJ/mol), and both are higher than those predicted for UB, UC, and UN. NBO calculations show strong ionic character for the ground states of UO and UF and bond orders that range from 2 to 3 and from 1 to 2, respectively. Comparisons of the calculated properties to those of the series comprising UB, UC, and UN diatomic molecules are given.