Magnetic and vibrational properties of the covalent chain antiferromagnet RbFeS₂

Ternary rubidium-iron sulfide, RbFeS 2 , belongs to a family of quasi-one-dimensional compounds with the general chemical composition A Fe Ch 2 (where A – K, Rb, Cs, Tl; Ch – S, Se). Understanding the magnetic properties of these compounds is a challenge. The controversy concerning the spin-state of the iron ion needs to be resolved to build the proper model of magnetism. Single crystals of RbFeS 2 were grown and characterized by powder x-ray diffraction. QD MPMS-5 SQUID magnetometry was used to measure the magnetic susceptibility, and specific heat was measured utilizing QD PPMS-9 setup. Above the transition to three-dimensional antiferromagnetic order at the Néel temperature of T N = 188 K, the susceptibility exhibits unusual quasi-linear increase up to the highest measured temperature of 500 K. The specific heat was measured in the temperature range 1.8 – 300 K. Ab initio phonon dispersion and density-of-states calculations were performed by means of density functional theory (DFT), and the calculated lattice specific heat was subtracted from the measured one giving the magnetic contribution to the specific heat. Our results suggest that the features of the magnetic specific heat are general for the whole family of the covalent chain ternary iron chalcogenides of the A Fe Ch 2 structure and indicate an intermediate S = 3/2 spin state of the iron ion.