PbV 2 O 6 under compression: near zero-linear compressibility and pressure-induced change in vanadium coordination.

This study presents evidence that lead metavanadate, PbV 2 O 6 , 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 PbV 2 O 6 (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 PbV 2 O 6 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 MgV 2 O 6 and ZnV 2 O 6 , the band gap of PbV 2 O 6 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.