Colossal Density-Driven Resistance Response in the Negative Charge Transfer Insulator MnS2
A reversible density driven insulator to metal to insulator transition in high-spin MnS_{2} is experimentally observed, leading with a colossal electrical resistance drop of 10^{8} Ω by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied S_{2}^{2-} σ_{3p}^{*} antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite (P2_{1}/c) is confirmed, and the bulk metallicity is broken with the system returning to an insula…
Coexistence of metamagnetism and slow relaxation of magnetization in ammonium hexafluoridorhenate.
The (NH4)2[ReF6] (1) salt was studied by X-ray diffraction, Raman spectroscopy, theoretical calculations, and magnetic measurements. 1 crystallizes in the trigonal space group Pm1 (Re–F = 1.958(5) A). In the Raman spectrum of 1, splitting of the observed peaks was observed and correlated to the valence frequencies of vibration of the [ReF6]2− anion. The study of the magnetic properties of 1, through DC and AC magnetic susceptibility measurements, reveals the coexistence of metamagnetism and slow relaxation of magnetization at low temperature, which is unusual in the molecular systems based on the paramagnetic 5d metal ions reported so far.
Decoupling lattice and magnetic instabilities in frustrated CuMnO$_2$
The $A$MnO$_{2}$ delafossites ($A$=Na, Cu), are model frustrated antiferromagnets, with triangular layers of Mn$^{3+}$~spins. At low temperatures ($T_{N}$=65 K), a $C2/m \rightarrow P\overline{1}$ transition is found in CuMnO$_2$, which breaks frustration and establishes magnetic order. In contrast to this clean transition, $A$=Na only shows short-range distortions at $T_N$. Here we report a systematic crystallographic, spectroscopic, and theoretical investigation of CuMnO$_2$. We show that, even in stoichiometric samples, non-zero anisotropic Cu displacements co-exist with magnetic order. Using X-ray/neutron diffraction and Raman scattering, we show that high pressures acts to decouple the…
CSD 1962857: Experimental Crystal Structure Determination
Related Article: James Louis-Jean, Samundeeswari M. Balasekaran, Keith V. Lawler, Adrián Sanchis-Perucho, José Martínez-Lillo, Dean Smith, Paul M. Forster, Ashkan Salamat, Frederic Poineau|2021|RSC Advances|11|6353|doi:10.1039/D0RA10325J