Norm-Conserving Pseudopotentials and Basis Sets to Explore Actinide Chemistry in Complex Environments

We have developed a new set of norm-conserving pseudopotentials and companion Gaussian basis sets for the actinide (An) series (Ac–Lr) using the Goedecker, Teter, and Hutter (GTH) formalism with the Perdew, Burke, and Ernzerhof (PBE) exchange–correlation functional of generalized gradient approximation. To test the accuracy and reliability of the newly parameterized An-GTH pseudopotentials and basis sets, a variety of benchmarks on actinide-containing molecules were carried out and compared to all-electron and available experimental results. The new pseudopotentials include both medium- ([Xe]4f14) and large-core ([Xe]4f145d10) options that successfully reproduce the structures and energetics, particularly redox processes. The medium-core size set, in particular, reproduces all-electron calculations over multiple oxidation states from 0 to VII, whereas the large-core set is suitable only for the early series elements and low oxidation states. The underlying reason for these transferability issues is discussed in detail. This work fills a critical void in the literature for studying the chemistry of 5f-block elements in the condensed phase.