Abstract
With broken-symmetry Kohn-Sham density functional theory calculations, it is demonstrated that the ferromagnetic or anti-ferromagnetic character of two prototypical binuclear copper complexes can be modified, both in the sign and in magnitude, by means of chemical substitutions operated on the bridges connecting the two magnetic centers. The level of detail provided by the magnetic exchange decomposition in terms of direct exchange, kinetic exchange, and core polarization puts forward the relative importance of the different bridges. At variance with the principal bridge for which chemical substitutions modify both the direct and the kinetic exchange contributions, modifications of the secondary bridge only affect the magnitude of the anti-ferromagnetic kinetic exchange mechanism, ultimately allowing for a direct control of the magnetic character of the modified compound.
Highlights
Magnetic exchange coupling J is one of the most important quantum interactions between two unpaired electrons.[1]
To what has been reported by other, our results available as Supporting Information indicate we can safely ignore them while retaining a good description of PATFIA and PATFOG magnetic properties
PATFIA and PATFOG feature two different bridges which chemical nature may modify the coupling between their two copper-centered magnetic electrons
Summary
Magnetic exchange coupling J is one of the most important quantum interactions between two (or more) unpaired electrons.[1] In the case of a finite-size systems, this interaction is important for designing molecular compounds with controlled magnetic properties. The determination of J, either experimentally[2,3,4] or by means of quantum-chemistry calculations,[5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20] is of tremendous importance for understanding the behavior of magnetic open-shell molecular systems. The Kohn-Sham density-functional theory combined with the so-called broken-symmetry approach (BS-KSDFT) is a popular and effective method which often provides semi-quantitative evaluations of J.7,15,22 By means of selective freezing of a subset of orbitals, some of the present authors recently introduced a decomposition scheme[23,24,25] which has been essentially applied to centro-symmetric molecules until now.[26]
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