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We present a combined experimental and density functional theory study that characterizes the charge and spin density in NiX2(3,5-lutidine)4(X= Cl, Br and I). In this material, magnetic exchange interactions occur via Ni2+–halide...halide–Ni2+pathways, forming one-dimensional chains. We find evidence for weak halide...halide covalency in the iodine system, which is greatly reduced whenX= Br and is absent forX= Cl; this is consistent with the reported `switching-on' of magnetic exchange in the larger-halide cases. Our results are benchmarked against density functional theory calculations on [NiHF2(pyrazine)2]SbF6, in which the primary magnetic exchange is mediated by F–H–F bridging ligands. This comparison indicates that, despite the largely depleted charge density found at the centre of halide...halide bonds, these through-space interactions can support strong magnetic exchange gated by weak covalency and enhanced by significant electron density overlapping that of the transition metal centres.
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Determining the anisotropy and exchange parameters of polycrystalline spin-1 magnets
Abstract Although low-dimensionalS = 1 antiferromagnets remain of great interest, difficulty in obtaining high-quality single crystals of the newest materials hinders experimental research in this area. Polycrystalline samples are more readily produced, but there are inherent problems in extracting the magnetic properties of anisotropic systems from powder data. Following a discussion of the effect of powder-averaging on various measurement techniques, we present a methodology to overcome this issue using thermodynamic measurements. In particular we focus on whether it is possible to characterise the magnetic properties of polycrystalline, anisotropic samples using readily available laboratory equipment. We test the efficacy of our method using the magnets [Ni(H2O)2(3,5-lutidine)4](BF4)2and Ni(H2O)2(acetate)2(4-picoline)2, which have negligible exchange interactions, as well as the antiferromagnet [Ni(H2O)2(pyrazine)2](BF4)2, and show that we are able to extract the anisotropy parameters in each case. The results obtained from the thermodynamic measurements are checked against electron-spin resonance and neutron diffraction. We also present a density functional method, which incorporates spin–orbit coupling to estimate the size of the anisotropy in [Ni(H2O)2(pyrazine)2](BF4)2.
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- Award ID(s):
- 1703003
- PAR ID:
- 10308325
- Author(s) / Creator(s):
- ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; more »
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- New Journal of Physics
- Volume:
- 21
- Issue:
- 9
- ISSN:
- 1367-2630
- Page Range / eLocation ID:
- Article No. 093025
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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