Hexagonal iron sulfide exhibits a fascinating coexistence of metal–insulator, structural and magnetic transitions, reflecting an intimate interplay of its spin, phonon and charge degrees of freedom. Here, we show how a subtle competition of energetic and entropic free-energy components governs its thermodynamics and the sequence of phase transitions it undergoes upon cooling. By means of comprehensive neutron and X-ray scattering measurements, and supported by first-principles electronic structure simulations, we identify the critical role of the coupling between antiferromagnetic ordering and instabilities of anharmonic phonons in the metallic phase in driving the metal–insulator transition. The antiferromagnetic ordering enables the emergence of two zone-boundary soft phonons, whose coupling to a zone-centre mode drives the lattice distortion opening the electronic bandgap. Simultaneously, spin–lattice coupling opens a gap in the magnon spectrum that controls the entropy component of the metal–insulator transition free energy. These results reveal the importance of spin–phonon coupling to tune anharmonic effects, thus opening new avenues to design novel technologically important materials harbouring the metal–insulator transition and magnetoelectric behaviours.
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We thank O. Hellman for providing access to and support with the TDEP software. Neutron and X-ray scattering measurements were supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under the Early Career award no. DE-SC0016166. Analysis of results and writing of the manuscript was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under award no. DE-SC0019978. H.Z. (sample synthesis) thanks the support from NSF-DMR-1350002. The use of Oak Ridge National Laboratory’s Spallation Neutron Source and High Flux Isotope Reactor was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US DOE. This research used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Theoretical calculations were performed using resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under contract no. DE-AC02-05CH11231.
The authors declare no competing interests.
Publisher’s noteSpringer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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Bansal, D., Niedziela, J.L., Calder, S. et al. Magnetically driven phonon instability enables the metal–insulator transition in h-FeS. Nat. Phys. 16, 669–675 (2020). https://doi.org/10.1038/s41567-020-0857-1
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