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

Lu, Jun-Bo; Cantu, David C.; Xu, Cong-Qiao; Nguyen, Manh-Thuong; Hu, Han-Shi; Glezakou, Vassiliki-Alexandra; Rousseau, Roger J.; Li, Jun

doi:10.1021/acs.jctc.1c00026

DOE OSTI · 1810108

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

Lu, Jun-Bo·Cantu, David C.·Xu, Cong-Qiao·Nguyen, Manh-Thuong·Hu, Han-Shi·Glezakou, Vassiliki-Alexandra·Rousseau, Roger J.·Li, Jun

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Abstract

We constructed and tested a new set of norm-conserving pseudopotentials, as well as companion Gaussian basis sets, for the actinide series (Ac–Lr) using the Goedecker, Teter and Hutter (GTH) formalism within the generalized gradient approximation (GGA) functional for exchange-correlation of Perdew, Burke and Ernzerhof (PBE). This fills a critical void in the literature for studying the chemistry of 5f–block elements in condensed phase. The accuracy and reliability of the newly parameterized An–GTH pseudopotentials and basis sets, a variety of tests on actinide-containing molecules were carried out and compared to all-electron and available experimental results. The new pseudopotentials include both medium ( [Xe]4f 14 ) and large core ( [Xe]4f 14 5d 10 ) options that successfully reproduced structure and energetics, particularly redox processes. The medium core size set, in particular, reproduced all electron calculations over multiple oxidation states from 0 to VII, whereas the large core set was suitable only for the early series elements and low oxidation states.

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Lu, Jun-Bo, Cantu, David C., Xu, Cong-Qiao, Nguyen, Manh-Thuong, Hu, Han-Shi, Glezakou, Vassiliki-Alexandra, Rousseau, Roger J., Li, Jun. 2021-05-25. Norm-Conserving Pseudopotentials and Basis Sets to Explore Actinide Chemistry in Complex Environments. https://doi.org/10.1021/acs.jctc.1c00026

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