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Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory.
J Chem Phys 2019; 151(13):134102JC

Abstract

We have examined the performance of Multiconfiguration Pair-Density Functional Theory (MC-PDFT) for computing the ground-state properties of actinide species. Specifically, we focused on the properties of UN2 and various actinyl species. The properties obtained with MC-PDFT at the scalar-relativistic level are compared to Kohn-Sham DFT (KS-DFT); complete active space self-consistent field theory, CASSCF; coupled-cluster theory, CCSD(T) and CCSDT; as well as multireference perturbation theory (CASPT2). We examine the degree to which MC-PDFT improves over KS-DFT and CASSCF while aligning with CASPT2, CCSD(T), and CCSDT. All properties that we considered were for the CASPT2 electronic ground states. For structural parameters, MC-PDFT confers very little advantage over KS-DFT, especially the B3LYP density functional. For NpO2 3+, MC-PDFT and local KS-DFT functionals excessively favor the bent structure, whereas CCSDT and CASPT2 predict the bent and linear structures as isoenergetic. For this special case, hybrid KS-DFT functionals like PBE0 and B3LYP provide results closer to CASPT2 and CCSDT than MC-PDFT. On a more positive note, MC-PDFT is very close to CASPT2 and CCSD(T) for the redox potentials, energetics of redox chemical reactions, as well as ligand-binding energies. These are encouraging results since MC-PDFT is more affordable. The best MC-PDFT functional is ft-PBE. Our findings suggest that MC-PDFT can be used to study systems and excited states with larger strong electron correlation effects than were considered here. However, for the systems and properties considered here, KS-DFT functionals do well, justifying their usage as the bulwark of computational actinyl chemistry over the last two to three decades.

Authors+Show Affiliations

Department of Chemistry, University of Nevada Reno, 1664 N. Virginia Street, Reno, Nevada 89557-0216, USA.Department of Chemistry, University of Nevada Reno, 1664 N. Virginia Street, Reno, Nevada 89557-0216, USA.Department of Chemistry, University of Nevada Reno, 1664 N. Virginia Street, Reno, Nevada 89557-0216, USA.Department of Chemistry, University of Nevada Reno, 1664 N. Virginia Street, Reno, Nevada 89557-0216, USA.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31594337

Citation

Adeyiga, Olajumoke, et al. "Ground-state Actinide Chemistry With Scalar-relativistic Multiconfiguration Pair-density Functional Theory." The Journal of Chemical Physics, vol. 151, no. 13, 2019, p. 134102.
Adeyiga O, Suleiman O, Dandu NK, et al. Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory. J Chem Phys. 2019;151(13):134102.
Adeyiga, O., Suleiman, O., Dandu, N. K., & Odoh, S. O. (2019). Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory. The Journal of Chemical Physics, 151(13), p. 134102. doi:10.1063/1.5099373.
Adeyiga O, et al. Ground-state Actinide Chemistry With Scalar-relativistic Multiconfiguration Pair-density Functional Theory. J Chem Phys. 2019 Oct 7;151(13):134102. PubMed PMID: 31594337.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory. AU - Adeyiga,Olajumoke, AU - Suleiman,Olabisi, AU - Dandu,Naveen K, AU - Odoh,Samuel O, PY - 2019/10/10/entrez PY - 2019/10/9/pubmed PY - 2019/10/9/medline SP - 134102 EP - 134102 JF - The Journal of chemical physics JO - J Chem Phys VL - 151 IS - 13 N2 - We have examined the performance of Multiconfiguration Pair-Density Functional Theory (MC-PDFT) for computing the ground-state properties of actinide species. Specifically, we focused on the properties of UN2 and various actinyl species. The properties obtained with MC-PDFT at the scalar-relativistic level are compared to Kohn-Sham DFT (KS-DFT); complete active space self-consistent field theory, CASSCF; coupled-cluster theory, CCSD(T) and CCSDT; as well as multireference perturbation theory (CASPT2). We examine the degree to which MC-PDFT improves over KS-DFT and CASSCF while aligning with CASPT2, CCSD(T), and CCSDT. All properties that we considered were for the CASPT2 electronic ground states. For structural parameters, MC-PDFT confers very little advantage over KS-DFT, especially the B3LYP density functional. For NpO2 3+, MC-PDFT and local KS-DFT functionals excessively favor the bent structure, whereas CCSDT and CASPT2 predict the bent and linear structures as isoenergetic. For this special case, hybrid KS-DFT functionals like PBE0 and B3LYP provide results closer to CASPT2 and CCSDT than MC-PDFT. On a more positive note, MC-PDFT is very close to CASPT2 and CCSD(T) for the redox potentials, energetics of redox chemical reactions, as well as ligand-binding energies. These are encouraging results since MC-PDFT is more affordable. The best MC-PDFT functional is ft-PBE. Our findings suggest that MC-PDFT can be used to study systems and excited states with larger strong electron correlation effects than were considered here. However, for the systems and properties considered here, KS-DFT functionals do well, justifying their usage as the bulwark of computational actinyl chemistry over the last two to three decades. SN - 1089-7690 UR - https://www.unboundmedicine.com/medline/citation/31594337/Ground-state_actinide_chemistry_with_scalar-relativistic_multiconfiguration_pair-density_functional_theory L2 - https://dx.doi.org/10.1063/1.5099373 DB - PRIME DP - Unbound Medicine ER -