Prediction and interpretation of the 57Fe isomer shift in Mössbauer spectra by 
density functional theory

Neese, Frank

doi:10.1016/S0020-1693(02)01031-9

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

Prediction and interpretation of the ⁵⁷Fe isomer shift in Mössbauer spectra by density functional theory

MPS-Authors

/persons/resource/persons216825

Neese, Frank
Research Department Wieghardt, Max Planck Institute for Radiation Chemistry, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Neese, F. (2002). Prediction and interpretation of the ⁵⁷Fe isomer shift in Mössbauer spectra by density functional theory. Inorganica Chimica Acta, 337, 181-192. doi:10.1016/S0020-1693(02)01031-9.

Cite as: https://hdl.handle.net/21.11116/0000-0007-F264-7

Abstract

The calibration of two popular density functionals (B3LYP and BP86) for the prediction of isomer shifts (IS) in ⁵⁷Fe Mössbauer (MB) spectra is reported. A linear correlation between non-relativistically calculated theoretical electron densities and experimentally measured ISs is established. Both functionals lead to accurate predictions of MB ISs with standard deviations on the order of approximately 0.1 mm s⁻¹ over a range of approximately 2 mm s⁻¹. The correlation holds for complexes of different total charge, total spin, valence state at the iron, coordination number and coordination geometry. A detailed analysis of the contributions to the IS is presented. It is shown that the important contributions are: (a) the variation of the 3s-contribution which is mainly caused by differing shielding according to the d-population of the metal; and (b) variations in the valence shell contribution. The latter contribution accounts for approximately 70% of the totally observed variation. The interpretation of the valence contribution is complex and involves contributions from changes in covalencies, orbital distortions due to bonding and shielding effects. The changes in metal-ligand distances are also an important factor, which influences the shape of the 4s-orbital and therefore modulates ISs.