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

A large set of neptunium compounds with different oxidation states (III to VII) was assembled to study the Mossbauer 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 Mossbauer isomer shifts. The CASPT2 calculations perform very satisfactorily. For a subset of Np compounds, both static and dynamic correlation effects were substantial. A rational active space selection based on orbital entanglement diagrams proved beneficial for determining the optimal reference wave function.

Automated summary

A study was conducted on a large set of neptunium compounds with different oxidation states to investigate the Mossbauer isomer shift. The study used wave function calculations and density matrix renormalization group algorithms to understand covalency in f-elements complexes. The researchers found that the calculations produced different orbital overlocalization errors for low and high Np oxidation states. Attempts to mitigate the errors using large active spaces were only partially successful, highlighting the need for explicit treatment of dynamic correlation. CASPT2 calculations performed well, and a rational active space selection proved beneficial for determining the optimal reference wave function.