PbV2O6 under compression: near zero-linear compressibility and pressure-induced change in vanadium coordination

Abstract

This study presents evidence that lead metavanadate, PbV₂O₆, is a material with zero-linear compressibility, which maintains its crystal size in one crystallographic direction even under external pressures of up to 20 GPa. The orthorhombic polymorph of PbV₂O₆ (space group Pnma) was studied up to 20 GPa using synchrotron powder X-ray diffraction, Raman spectroscopy, and density-functional theory simulations to investigate its structural and vibrational evolution under compression. Up to this pressure we find no evidence of any structural phase transitions by any diagnostic technique, however, a progressive transformation of the coordination polyhedron of vanadium atoms is revealed which results in the zero-linear compressibility. High-pressure Raman experiments enabled the identification and symmetry assignation of all 54 zone-centre Raman-active modes as well as the calculation of their respective pressure coefficients. Three independent high-pressure powder X-ray diffraction experiments were performed using different pressure-transmitting media (Ne, 4 : 1 methanol–ethanol mixture, and silicone oil). The results show a high anisotropic behaviour in the linear compressibility of the crystallographic axes. The PbV₂O₆ bulk modulus of 86.1(9) GPa was determined using a third-order Birch-Murnaghan equation of state. The experimental results are supported by ab initio density-functional theory calculations, which provide vibrational patterns, unit-cell parameters, and atomic positions. These calculations also reveal that, unlike MgV₂O₆ and ZnV₂O₆, the band gap of PbV₂O₆ closes with pressure at a rate of −54 meV GPa⁻¹ due to the contribution of the Pb 6s orbital to the top of the valence band.