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Single Crystal X‐ray Structure Investigation and Electronic Structure Studies of La‐Deficient Nickel Stannide La 4.87 Ni 12 Sn 24 Grown from Sn Flux
Author(s) -
Zhuravleva Marina A.,
Bilc Daniel,
Mahanti S. D.,
Kanatzidis Mercouri G.
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200390052
Subject(s) - diamagnetism , crystallography , crystal structure , nickel , paramagnetism , magnetic susceptibility , fermi level , pauli exclusion principle , electronic structure , single crystal , metal , density of states , materials science , electron , chemistry , condensed matter physics , physics , magnetic field , quantum mechanics , metallurgy
The cubic La 4.87 Ni 12 Sn 24 was synthesized in reactions involving liquid Sn. The compound crystallizes in the cubic syngony, space group Im 3¯, Z = 2, cell parameter a = 11.9662(14) Å, and is related to the Gd 3 Ni 8 Sn 16 structure type previously refined from powder X‐ray data. The crystal structure of La 4.87 Ni 12 Sn 24 was solved and refined using single crystal X‐ray data to final R 1 = 2.67%, w R 2 = 6.92%. The refinement showed no mixed occupancy with Sn for the La(1) site, contrary to what was proposed for Gd 3 Ni 8 Sn 16 . Instead, a partial occupancy of 87% was detected for the La(1) at 2a . Electronic structure calculations show that the system is metallic, and the density of states at the Fermi level falls at a peak with the highest contribution coming from La(1) atoms, if the compound with ideal occupancies La 5 Ni 12 Sn 24 is assumed. The deficiency of the La(1) site could therefore originate in the lowering of the total energy of the system due to the loss of 0.39 electrons per formula unit. Magnetic measurement data indicates nearly temperature independent Pauli paramagnetism. Theoretical estimation of the magnetic susceptibility after including core diamagnetic corrections agrees well with experiment.