Observation of the asphericity of 4f-electron density and its relation to the magnetic anisotropy axis in single-molecule magnets

The distribution of electrons in the 4f orbitals of lanthanide ions is often assigned a crucial role in the design of single-molecule magnets, which maintain magnetization in zero external field. Optimal spatial complementarity between the 4f-electron density and the ligand field is key to maximizin...

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Bibliographic Details
Published in:Nature chemistry Vol. 12; no. 2; pp. 213 - 219
Main Authors: Gao, Chen, Genoni, Alessandro, Gao, Song, Jiang, Shangda, Soncini, Alessandro, Overgaard, Jacob
Format: Journal Article
Language:English
Published: England Nature Publishing Group 01.02.2020
Subjects:
Anisotropy
Asphericity
Axes (reference lines)
Complementarity
Density distribution
Dysprosium
Electron density
Electronic structure
Electrons
Magnetic anisotropy
Magnets
Molecular structure
Multipoles
Optimization
Synchrotron radiation
Wave functions
X-ray diffraction
ISSN:1755-4330, 1755-4349, 1755-4349
Online Access:Get full text
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Summary:The distribution of electrons in the 4f orbitals of lanthanide ions is often assigned a crucial role in the design of single-molecule magnets, which maintain magnetization in zero external field. Optimal spatial complementarity between the 4f-electron density and the ligand field is key to maximizing magnetic anisotropy, which is an important factor in the ability of lanthanide complexes to display single-molecule magnet behaviour. Here we have experimentally determined the electron density distribution in two dysprosium molecular complexes by interpreting high-resolution synchrotron X-ray diffraction with a multipole model. The ground-state 4f-electron density is found to be an oblate ellipsoid, as is often deduced from a simplified Sievers model that assumes a pure |±15/2> ground-state doublet for the lanthanide ion. The large equatorial asymmetry-determined by a model wavefunction-was found to contain considerable M mixing of |±11/2> and only 81% of |±15/2>. The experimental molecular magnetic easy axes were recovered, and found to deviate by 13.1° and 8.7° from those obtained by ab initio calculations.
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ISSN:1755-4330
1755-4349
1755-4349
DOI:10.1038/s41557-019-0387-6