Mott metal-insulator transitions in pressurized layered trichalcogenides

Abstract: Transition metal phosphorous trichalcogenides, $M{\rm P}X_3$ ($M$ and $X$ being transition metal and chalcogen elements respectively), have been the focus of substantial interest recently because of their possible magnetism in the two-dimensional limit. Here we investigate material properties of the compounds with $M$ = Mn and Ni employing $\textit{ab-initio}$ density functional and dynamical mean-field calculations, especially their electronic behavior under external pressure in the paramagnetic phase. Mott metal-insulator transitions (MIT) are found to be a common feature for both compounds, but their lattice structures show drastically different behaviors depending on the relevant orbital degrees of freedom, i.e. $t_{\rm 2g}$ or $e_{g}$. MnPS$3$ undergoes an isosymmetric structural transition by forming Mn-Mn dimers due to the strong direct overlap between the neighboring $t{\rm 2g}$ orbitals, accompanied by a significant volume collapse and a spin-state transition. In contrast, NiPS$_3$ and NiPSe$_3$, with their active $e_g$ orbital degrees of freedom, do not show a structural change at the MIT pressure or deep in the metallic phase. Hence NiPS$_3$ and NiPSe$_3$ become rare examples of materials hosting electronic bandwidth-controlled Mott MITs, thus showing promise for ultrafast resistivity switching behavior.