Structural transition in the magnetoelectricZnCr2Se4spinel under pressure

Abstract

Τhe magnetoelectric $\mathrm{ZnC}{\mathrm{r}}_{2}\mathrm{S}{\mathrm{e}}_{4}$ spinel, with space group $Fd\overline{3}m$, undergoes a reversible first-order structural transition initiating at 17 GPa, as revealed by our high-pressure x-ray diffraction studies at room temperature. We tentatively assign the high-pressure modification to an $A\mathrm{M}{\mathrm{o}}_{2}{\mathrm{S}}_{4}$-type phase, a distorted variant of the monoclinic $\mathrm{C}{\mathrm{r}}_{3}{\mathrm{S}}_{4}$ structure. Furthermore, our Raman investigation provides evidence for a pressure-induced insulator-metal transition. Our density functional theory calculations successfully reproduce the structural transition. They indicate significant band gap and magnetic moment reduction accompanying the pressure-induced structural modification. We discuss our findings in conjunction with the available high-pressure results on other Cr-based chalcogenide spinels.