Considering Density Functional Approaches for Actinide Species: The An66 Molecule Set

The importance of spin-orbit effects on the predictions of energetic properties of actinide compounds has been considered for 18 different density functionals, comparing the spin-orbit and non-spin-orbit (standard) forms of density functional theory (DFT). A set of enthalpies of formation for 66 small actinide (Th-Am) compounds-the An66 set, for which experimental data are available-have been investigated. The set includes actinide halides, oxides, and oxohalides in the general form AnO(m)X(n), where n = 0-6, m = 0-3, and X = F, Cl, Br, or I. The impact of basis set choice was investigated, and to help account for the impact of relativity, the Stuttgart general and segmented contracted atomic natural orbital (ANO) basis sets paired with small core relativistic effective core potentials (RECP) as well as all-electron calculations utilizing the third-order Douglas-Kroll-Hess were considered.

Automated summary

This study compared the effects of 18 different density functionals on the predictions of energetic properties of actinide compounds, specifically focusing on the importance of spin-orbit effects. Investigating a set of 66 small actinide compounds, it was found that both spin-orbit effects and basis set choice played a role in the accuracy of predictions, with the need to consider relativistic effects.