Synthesis, Crystal and Electronic Structure of the Quaternary Magnetic EuTAl4Si2 (T = Rh and Ir) Compounds
datasetposted on 03.02.2014, 00:00 authored by Arvind Maurya, Arumugam Thamizhavel, Alessia Provino, Marcella Pani, Pietro Manfrinetti, Durga Paudyal, Sudesh Kumar Dhar
Single crystals of the quaternary europium compounds EuRhAl4Si2 and EuIrAl4Si2 were synthesized by using the Al–Si binary eutectic as a flux. The structure of the two quaternary compounds has been refined by single crystal X-ray diffraction. Both compounds are stoichiometric and adopt an ordered derivative of the ternary KCu4S3 structure type (tetragonal tP8, P4/mmm). The two compounds reported here represent the first example of a quaternary and truly stoichiometric 1:1:4:2 phase crystallizing with this structure type. In light of our present results, the structure of the BaMg4Si3 compound given in literature as representing a new prototype is actually isotypic with the KCu4S3 structure. Local spin density approximation including the Hubbard U parameter (LSDA + U) calculations show that Eu ions are in the divalent state, with a significant hybridization between the Eu 5d, Rh (Ir) 4d (5d), Si 3p and Al 3p states. Magnetic susceptibility measured along the  direction confirms the divalent nature of the Eu ions in EuRhAl4Si2 and EuIrAl4Si2, which order magnetically near ∼11 and ∼15 K, respectively.