High-temperature magnetostructural transition in van der Waals-layered a-MoCl3

Abstract

The crystallographic and magnetic properties of the cleavable 4d3 transition metal compound a-MoCl3 are reported, with a focus on the behavior above room temperature. Crystals were grown by chemical vapor transport and characterized using temperature dependent x-ray diffraction, Raman spectroscopy, and magnetization measurements. A structural phase transition occurs near 585 K, at which the Mo-Mo dimers present at room temperature are broken. A nearly regular honeycomb net of Mo is observed above the transition, and an optical phonon associated with the dimerization instability is identified in the Raman data and in first-principles calculations. The crystals are diamagnetic at room temperature in the dimerized state, and the magnetic susceptibility increases sharply at the structural transition. Moderately strong paramagnetism in the high-temperature structure indicates the presence of local moments on Mo. This is consistent with results of spin-polarized density functional theory calculations using the low- and high-temperature structures. Above the magnetostructural phase transition the magnetic susceptibility continues to increase gradually up to the maximum measurement temperature of 780 K, with a temperature dependence that suggests two-dimensional antiferromagnetic correlations.

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• Pressure-induced collapse of spin-orbital Mott state in the hyperhoneycomb iridate $\beta$-Li${}_2$IrO${}_3$
• Pressure-induced structural dimerization in the hyperhoneycomb iridate $\beta$-Li${}_2$IrO${}_3$ at low temperatures
• Self-selecting vapor growth of transition metal halide single crystals
• Dimerization in honeycomb Na2RuO3 under pressure: a DFT study
• Doping effects on the valence bond solid of Li${}_2$RuO${}_3$ with Mn substitution
• Observation of a new polyhalide phase in Ag-Cl${}_2$ system at high pressure