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

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

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)3360-3371
Number of pages12
JournalJournal of Chemical Theory and Computation
Volume17
Issue number6
DOIs
StatePublished - Jun 8 2021
Externally publishedYes

Funding

J.-B.L., C.-Q.X., H.-S.H., and J.L. were supported by the National Natural Science Foundation of China (nos. 22033005 and 21590792). D.C.C. acknowledges support from the Vice Presidency for Research and Innovation, and the College of Engineering, of the University of Nevada, Reno. R.R. and M.-N. T. acknowledge support from Pacific Northwest National Laboratory (PNNL) directed research and development for the chemistry of molten salt reactors (CheMSR) agile initiative. V.A.G. acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences and Biosciences Division, project 72353 (Interfacial Structure and Dynamics in Ion Separations). PNNL is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. This work is also partially sponsored by the Guangdong Provincial Key Laboratory of Catalysis (no. 2020B121201002). The authors gratefully acknowledge computational resources from SUSTech Supercomputer Center, Tsinghua National Laboratory for Information Science and Technology, PNNL's Research Computing (RC) and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231.

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