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Issue 17, 2015
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Benchmark study of the Mössbauer isomer shifts of Eu and Np complexes by relativistic DFT calculations for understanding the bonding nature of f-block compounds

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Abstract

We have performed benchmark investigations into the bonding properties in lanthanide and actinide complexes to quantitatively estimate the covalency of f-block compounds. Three different density functionals including BP86 (pure-GGA), B3LYP (hybrid-GGA) and B2PLYP (double hybrid-GGA) were employed for all-electron self-consistent field calculations compensated by the scalar-relativistic zero-order regular approximation (ZORA) Hamiltonian with a relativistically contracted all-electron basis set. Ten Eu and ten Np complexes were employed as benchmark sets for the calculation of Mössbauer parameters for 151Eu and 237Np compounds. As a result of the linear fitting between the calculated electron densities at the nucleus (ρcalc0) and the experimental isomer shifts (δexp), the calculations performed using the all-electron ZORA-B2PLYP level reproduced a change of electron density at the Mössbauer nucleus for both Eu and Np complexes with high correlation coefficients (R2 > 0.90). Mulliken's population analyses indicated that the BP86 and B3LYP methods overestimated the covalency of both Eu and Np complexes due to the smaller amount of the exact Hartree–Fock exchange admixture included in BP86 and B3PLYP compared to that in the B2PLYP functional. By comparing Mulliken's electronic structure analyses with the experimental isomer shifts, we found that Mulliken's spin population values were good parameters to quantitatively estimate the bonding natures of Eu and Np complexes.

Graphical abstract: Benchmark study of the Mössbauer isomer shifts of Eu and Np complexes by relativistic DFT calculations for understanding the bonding nature of f-block compounds

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Publication details

The article was received on 04 Oct 2014, accepted on 18 Mar 2015 and first published on 18 Mar 2015


Article type: Paper
DOI: 10.1039/C4DT03064H
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Citation: Dalton Trans., 2015,44, 8080-8088

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    Benchmark study of the Mössbauer isomer shifts of Eu and Np complexes by relativistic DFT calculations for understanding the bonding nature of f-block compounds

    M. Kaneko, S. Miyashita and S. Nakashima, Dalton Trans., 2015, 44, 8080
    DOI: 10.1039/C4DT03064H

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