Unusual Mott transition in multiferroic PbCrO3

The Mott insulator in correlated electron systems arises from classical Coulomb repulsion between carriers to provide a powerful force for electron localization. Turning such an insulator into a metal, the so-called Mott transition, is commonly achieved by “bandwidth” control or “band filling.” However, both mechanisms deviate from the original concept of Mott, which attributes such a transition to the screening of Coulomb potential and associated lattice contraction. Here, we report a pressure-induced isostructural Mott transition in cubic perovskite PbCrO₃. At the transition pressure of ∼3 GPa, PbCrO₃ exhibits significant collapse in both lattice volume and Coulomb potential. Concurrent with the collapse, it transforms from a hybrid multiferroic insulator to a metal. For the first time to our knowledge, these findings validate the scenario conceived by Mott. Close to the Mott criticality at ∼300 K, fluctuations of the lattice and charge give rise to elastic anomalies and Laudau critical behaviors resembling the classic liquid–gas transition. The anomalously large lattice volume and Coulomb potential in the low-pressure insulating phase are largely associated with the ferroelectric distortion, which is substantially suppressed at high pressures, leading to the first-order phase transition without symmetry breaking.Early transition-metal (TM) oxides with partially filled d electrons are strongly correlated (1, 2). Such correlated systems often present exciting new physics and technologically useful electronic and magnetic properties. Mott transition, characterized by delocalization of d electrons, is an attractive phenomenon for exploring the correlated nature of electrons (2, 3). Since the early failure of band theory in the 1930s, the Coulomb repulsion (U) has been proposed to be a strong force that causes electron localization (4, 5). In such electrostatic interaction, the repulsion energy decreases with the compressed lattice because of the screening effect (5–7). Consequently, as originally predicted by Mott (5), the Mott transition is controlled by U at pressures (P).Despite several decades of intensive study, it is still challenging to experimentally validate this view of Mott transition, because U is experimentally difficult to determine, and for most correlated materials it is independent of the pressure. For the known Mott systems, they are found to be controlled by either the bandwidth [e.g., the organic compound κ-Cl (8–10) and Cr-doped V₂O₃ (11, 12)] or band filling (i.e., doping of charge carriers into the parent insulator) (2). Recently, electronic transitions have frequently been reported in late 3d TM oxides (e.g., MnO) (13–16), which are theoretically attributed to bandwidth control (15) or crystal-field splitting (17). For those oxides, a U-controlled mechanism has also been proposed by Gavriliuk et al. (14) and Gavriliuk and coworkers (18); however, the spin cross-over, instead of the screening effect, is believed to contribute to the decreased U (14, 18). Complicating matter further is that the U of (Mg_1–xFe_x)O was computed to increase with pressures (13).TM oxides with a perovskite structure (ABO₃) often exhibit intriguing structural, magnetic, and electronic properties for the study of correlated systems. Among them, PbCrO₃ is such a material that can only be synthesized at high pressures. At ambient pressure, it adopts a paramagnetic (PM), cubic structure at room temperature (T) with an anomalously large unit-cell volume and transforms to an antiferromagnetic (AFM) ground state at low temperatures (19, 20). The magnetic properties arise from unpaired 3d electrons in Cr (i.e., nominally 3d²) with a large U value of 8.28 eV (19–21). Under high pressures, an isostructural phase transition (i.e., no symmetry breaking) has recently been reported in PbCrO₃ with ∼9.8% volume reduction at ∼1.6 GPa; it is the largest volume reduction known in transition-metal oxides (22). Compared with the low-P phase, the high-P phase possesses a more “normal” unit-cell volume (see refs. 21 and 22) and a moderate U of ∼3 eV (23), suggesting a collapse of Coulomb repulsion energy at the phase transition. Because of the reduced U, the mobility of 3d electrons at high pressures is energetically more favorable, which would lead to d-electron delocalization. Apparently, this is a U-driven Mott transition in PbCrO₃ as conceived by Mott. However, to date, the electronic properties of both PbCrO₃ phases have only poorly been explored. In particular, controversial electronic states, including semiconductor (24, 25), half-metal (21), or insulator (20), have been reported for the low-P phase. Besides, the crystal structure and elastic and magnetic properties, as well as the underlying mechanism for the isostructural transition, are still unsettled issues, calling for rigorous investigation into this material.With these aims, in this work we present a comprehensive study on PbCrO₃ with a focus on the P-induced electronic transition. Our findings unveil a unique Mott transition in this perovskite and a new mechanism underlying the isostructural transition.