Relativistic density functional investigation of UX6 (X = F, Cl, Br and I)

Abstract

The molecular structures and the vibrational frequencies of uranium hexahalides UX6 (X = F, Cl, Br and I) molecules are investigated by using local density approximation (LDA) and generalised gradient approximation (GGA) functions (BP, BLYP and RPBE) in combination with two different relativistic methods (scalar and scalar + spin–orbit relativistic effects). The calculated results show that the differences are trivial between scalar and scalar+spin–orbit relativistic methods. The vibrational frequencies are also compared with existing experimental values, and overall, the RPBE approach gives the smallest error. The bond dissociation energies (BDEs) of UX6 are computed by using the RPBE function, thereby obtaining exact vibrational frequencies. In addition, the calculated magnitudes of the spin–orbit effect on the BDE of UX6 (X = F, Cl, Br, and I) are found to be approximately −0.3198, −0.3218, −0.3609 and −0.4415 eV, respectively.