A Comparative Relativistic DFT and Ab Initio Study on the Structure and Thermodynamics of the Oxofluorides of Uranium(IV), (V) and (VI)

All the possible uranium(VI, V, IV) oxides, fluorides and oxofluorides were studied theoretically by using density functional theory (DFT) in the generalised gradient approximation (GGA), and three different relativistic methods (all‐electron scalar four component Dyall RESC method (AE), relativistic small‐core ECPs, and zeroth order regular approximation ZORA). In order to test different correlation methods, for the two former relativistic methods hybrid DFT, and, for the AE method, MP2 molecular orbital calculations were performed as well. Single‐point AE‐CCSD(T) energies were calculated on MP2 geometries as well. Energies of the uranium(VI) and (V) oxofluorides dissociation, uranium(VI) fluoride hydrolysis and oxofluoride disproportionation were calculated and compared against the available experimental thermochemical data. AE‐CCSD(T) energies were the closest to the experiment. For GGA DFT methods, all the relativistic methods used yield similar results. For thermochemistry, the best quantitative agreement with the experimental and CCSD(T) values for both UO and UF bond strengths was obtained with hybrid DFT methods, provided that a reliable basis set was used. Both the GGA DFT and MP2 MO methods show overbinding of these bonds; moreover, this overbinding was found to be not uniform but strongly dependent on the coordination environment of the uranium atom in each case. UO vibrational frequencies given by hybrid DFT, however, are systematically overestimated, and are better reproduced by GGA DFT; MP2 values usually fall in‐between. Reaction enthalpies, UO frequencies and complex geometries given by the PBE, MPBE, BPBE, BLYP and OLYP GGA functionals are quite similar, with OLYP performing slightly better than the others but still not as good as hybrid DFT. The geometries of the molecules are found to be influenced by the following factors: the inverse transinfluence (ITI) of the oxygen ligand and, for UV, and UIV, the Jahn–Teller distortion. Benchmarking theoretical methods as applied to actinide molecules. All possible uranium(VI, V, IV) oxofluorides (such as UOF3 shown here) and their reactions have been used to benchmark quantum‐chemical methods including DFT, MP2, CCSD(T) as combined with three different relativistic approximations.