237Np Mössbauer Isomer Shifts: A Lesson About the Balance of Static and Dynamic Electron Correlation in Heavy Element Complexes

Motta, Laura C.; Autschbach, Jochen

doi:10.1021/acs.jctc.2c00194

²³⁷Np Mössbauer Isomer Shifts: A Lesson About the Balance of Static and Dynamic Electron Correlation in Heavy Element Complexes

Journal Article · Fri May 20 00:00:00 EDT 2022 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.2c00194· OSTI ID:2478533

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University at Buffalo, State University of New York, NY (United States)

A large set of neptunium compounds with different oxidation states (III to VII) was assembled to study the Mössbauer isomer shift by wave function calculations and better understand covalency in f-elements complexes. The contact density approach was used to calculate the isomer shift using complete active space self-consistent field (CASSCF) multiconfiguration wave functions, as well as matrix product states [from Density Matrix Renormalization Group (DMRG) algorithms] for large active spaces. Dynamic correlation effects for the isomer shifts were treated via CASPT2 energy derivatives with respect to the nuclear radius. The CASSCF calculations appear to produce different orbital overlocalization errors for low and high Np oxidation states. For compounds with low Np oxidation numbers, the errors can be attributed to the overlocalization of the 5f orbitals. For the compounds with high Np oxidation numbers, the main errors arise from an overlocalization of ligand orbitals and concomitant to weak donation bonding. Attempts to mitigate the overlocalization errors with large active spaces using DMRG were only partially successful, showing that explicit treatment of dynamic correlation is necessary for accurate predictions of Mössbauer isomer shifts. The CASPT2 calculations perform very satisfactorily. For a subset of Np compounds, both static and dynamic correlation effects were substantial. Furthermore, a rational active space selection based on orbital entanglement diagrams proved beneficial for determining the optimal reference wave function.

View Accepted Manuscript (DOE)

Research Organization:: University at Buffalo, State University of New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001136

OSTI ID:: 2478533

Alternate ID(s):: OSTI ID: 1977930

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 6 Vol. 18; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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