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Ising-type Magnetic Anisotropy in CePd2As2.

ABSTRACT: We investigated the anisotropic magnetic properties of CePd2As2 by magnetic, thermal and electrical transport studies. X-ray diffraction confirmed the tetragonal ThCr2Si2-type structure and the high-quality of the single crystals. Magnetisation and magnetic susceptibility data taken along the different crystallographic directions evidence a huge crystalline electric field (CEF) induced Ising-type magneto-crystalline anisotropy with a large c-axis moment and a small in-plane moment at low temperature. A detailed CEF analysis based on the magnetic susceptibility data indicates an almost pure |±5/2〉 CEF ground-state doublet with the dominantly |±3/2〉 and the |±1/2〉 doublets at 290 K and 330 K, respectively. At low temperature, we observe a uniaxial antiferromagnetic (AFM) transition at T N = 14.7 K with the crystallographic c-direction being the magnetic easy-axis. The magnetic entropy gain up to T N reaches almost R ln 2 indicating localised 4 f-electron magnetism without significant Kondo-type interactions. Below T N , the application of a magnetic field along the c-axis induces a metamagnetic transition from the AFM to a field-polarised phase at μ 0 H c0 = 0.95 T, exhibiting a text-book example of a spin-flip transition as anticipated for an Ising-type AFM.

SUBMITTER: Ajeesh MO

PROVIDER: S-EPMC5544730 | biostudies-other | 2017 Aug

REPOSITORIES: biostudies-other

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Project description:While the blocking barrier (U eff) and blocking temperature (T B) for "Dysprocenium" SIMs have been increased beyond liquid N2 temperature, device fabrication of these molecules remains a challenge as low-coordinate Ln3+ complexes are very unstable. Encapsulating the lanthanide ion inside a cage such as a fullerene (called endohedral metallofullerene or EMF) opens up a new avenue leading to several Ln@EMF SMMs. The ab initio CASSCF calculations play a pivotal role in identifying target metal ions and suitable cages in this area. Encouraged by our earlier prediction on Ln2@C79N, which was verified by experiments, here we have undertaken a search to enhance the exchange coupling in this class of molecules beyond the highest reported value. Using DFT and ab initio calculations, we have studied a series of Gd2@C2n (30 ≤ 2n ≤ 80), where an antiferromagnetic J Gd⋯Gd of -43 cm-1 was found for a stable Gd2@C38-D 3h cage. This extremely large and exceptionally rare 4f⋯4f interaction results from a direct overlap of 4f orbitals due to the confinement effect. In larger cages such as Gd2@C60 and Gd2@C80, the formation of two centre-one-electron (2c-1e-) Gd-Gd bonds is perceived. This results in a radical formation in the fullerene cage leading to its instability. To avoid this, we have studied heterofullerenes where one of the carbon atoms is replaced by a nitrogen atom. Specifically, we have studied Ln2@C59N and Ln2@C79N, where strong delocalisation of the electron yields a mixed valence-like behaviour. This suggests a double-exchange (B) is operational, and CASSCF calculations yield a B value of 434.8 cm-1 and resultant J Gd-rad of 869.5 cm-1 for the Gd2@C59N complex. These parameters are found to be two times larger than the world-record J reported for Gd2@C79N. Further ab initio calculations reveal an unprecedented U cal of 1183 and 1501 cm-1 for Dy2@C59N and Tb2@C59N, respectively. Thus, this study offers strong exchange coupling as criteria for new generation SMMs as the existing idea of enhancing the blocking barrier via crystal field modulation has reached its saturation point.

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Ising-type Magnetic Anisotropy in CePd2As2.

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