Quantification of the Magnetic Anisotropy of a Single-Molecule Magnet from the Experimental Electron Density |
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Authors: | Emil Damgaard-Møller Dr. Lennard Krause Kasper Tolborg Dr. Giovanni Macetti Dr. Alessandro Genoni Prof. Jacob Overgaard |
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Affiliation: | 1. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark;2. Université de Lorraine & CNRS, Laboratoire de Physique et Chimie Théoriques (LPCT), UMR CNRS 7019, 1 Boulevard Arago, F-57078 Metz, France |
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Abstract: | Reported here is an entirely new application of experimental electron density (EED) in the study of magnetic anisotropy of single-molecule magnets (SMMs). Among those SMMs based on one single transition metal, tetrahedral CoII-complexes are prominent, and their large zero-field splitting arises exclusively from coupling between the d and dxy orbitals. Using very low temperature single-crystal synchrotron X-ray diffraction data, an accurate electron density (ED) was obtained for a prototypical SMM, and the experimental d-orbital populations were used to quantify the dxy-d coupling, which simultaneously provides the composition of the ground-state Kramers doublet wave function. Based on this experimentally determined wave function, an energy barrier for magnetic relaxation in the range 193–268 cm−1 was calculated, and is in full accordance with the previously published value of 230 cm−1 obtained from near-infrared spectroscopy. These results provide the first clear and direct link between ED and molecular magnetic properties. |
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Keywords: | cobalt electron density magnetic properties single-molecule studies X-ray diffraction |
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