Density Functional Theory Approach to the Vibrational Properties and Magnetic Specific Heat of the Covalent Chain Antiferromagnet KFeS2.

Ternary potassium-iron sulfide, KFeS2, belongs to the family of highly anisotropic quasi-one-dimensional antiferromagnets with unusual "anti-Curie-Weiss" susceptibility, quasi-linearly growing with a rising temperature up to 700 K, an almost vanishing magnetic contribution to the specific heat, drastically reduced magnetic moment, etc. While some of the measurements can be satisfactorily described, the deficiency of the entropy changes upon the magnetic transition and the spin state of the iron ion remains a challenge for the further understanding of magnetism. In this work, high-quality single-crystalline samples of KFeS2 were grown by the Bridgman method, and their stoichiometry, crystal structure, and absence of alien magnetic phases were checked, utilizing wave-length dispersive X-ray electron-probe microanalysis, powder X-ray diffraction, and 57Fe Mössbauer spectroscopy, respectively. An ab initio approach was developed to calculate the thermodynamic properties of KFeS2. The element-specific phonon modes and their density of states (PDOS) were calculated applying the density functional theory in the DFT + U version, which explicitly takes into account the on-site Coulomb repulsion U of electrons and their exchange interaction J. The necessary calibration of the frequency scale was carried out by comparison with the experimental iron PDOS derived from the inelastic nuclear scattering experiment. The infrared absorption measurements confirmed the presence of two high-frequency peaks consistent with the calculated PDOS. The calibrated PDOS allowed the calculation of the lattice contribution to the specific heat of KFeS2 by direct summation over the phonon modes without approximations and adjustable parameters. The temperature-dependent magnetic specific heat evaluated by subtraction of the calculated phonon contribution from the experimental specific heat provides a lower boundary for estimating the reduced spin state of the iron ion.

Manipulating surface magnetic order in iron telluride.

Control of emergent magnetic orders in correlated electron materials promises new opportunities for applications in spintronics. For their technological exploitation, it is important to understand the role of surfaces and interfaces to other materials and their impact on the emergent magnetic orders. Here, we demonstrate for iron telluride, the nonsuperconducting parent compound of the iron chalcogenide superconductors, determination and manipulation of the surface magnetic structure by low-temperature spin-polarized scanning tunneling microscopy. Iron telluride exhibits a complex structural and magnetic phase diagram as a function of interstitial iron concentration. Several theories have been put forward to explain the different magnetic orders observed in the phase diagram, which ascribe a dominant role either to interactions mediated by itinerant electrons or to local moment interactions. Through the controlled removal of surface excess iron, we can separate the influence of the excess iron from that of the change in the lattice structure.