Rules and mechanisms governing octahedral tilts in perovskites under pressure

Abstract

The rotation of octahedra (octahedral tilting) is common in ABO3 perovskites and relevant to many physical phenomena, ranging from electronic and magnetic properties, metal-insulator transitions to improper ferroelectricity. Hydrostatic pressure is an efficient way to tune and control octahedral tiltings. However, the pressure behavior of such tiltings can dramatically differ from one material to another, with the origins of such differences remaining controversial. In this work, we discover several new mechanisms and formulate a set of simple rules that allow to understand how pressure affects oxygen octahedral tiltings, via the use and analysis of first-principles results for a variety of compounds. Besides the known A-O interactions, we reveal that the interactions between specific B-ions and oxygen ions contribute to the tilting instability. We explain the previously reported trend that the derivative of the oxygen octahedral tilting with respect to pressure (dR/dP) usually decreases with both the tolerance factor and the ionization state of the A-ion, by illustrating the key role of A-O interactions and their change under pressure. Furthermore, three new mechanisms/rules are discovered. We further predict that the polarization associated with the so-called hybrid improper ferroelectricity could be manipulated by hydrostatic pressure, by indirectly controlling the amplitude of octahedral rotations.

arXiv commentSubmitted to Phys. Rev

References in corpus (11)

• Colossal Magnetoresistant Materials: The Key Role of Phase Separation
• Multiferroicity, The coupling between magnetic and polarization
• Octahedral rotation-induced ferroelectricity in cation ordered perovskites
• First-principles predictions of low-energy phases of multiferroic BiFeO3
• Pressure-temperature phase diagram of SrTiO3 up to 53 GPa
• Ab initio Evidence for Giant Magnetoelectric Responses Driven by Structural Softness
• Predicting a Ferrimagnetic Phase of Zn2FeOsO6 with Strong Magnetoelectric Coupling
• High-pressure investigations of CaTiO3 up to 60 GPa using X-ray diffraction and Raman spectroscopy
• Effect of pressure on octahedral distortions in RCrO3 (R = Lu, Tb, Gd, Eu, Sm): The role of R-ion size and its implications
• Room-Temperature Ferrimagnet with Frustrated Antiferroelectricity: Promising Candidate Toward Multiple State Memory
• The electronic structures and magnetic properties of perovskite ruthenates from constrained orbital hybridization calculations

Cited by in corpus (13)

• Energetics of oxygen-octahedra rotations in perovskite oxides from first principles
• Soft antiphase tilt of oxygen octahedra in the hybrid improper multiferroic Ca3Mn1.9Ti0.1O7
• Thermal conductivity of perovskite KTaO3 and PbTiO3 from first principles
• Crossover in the pressure evolution of elementary distortions in RFeO3 perovskites and its impact on their phase transition
• Pressure-induced enhancement of non-polar to polar transition temperature in metallic LiOsO${}_3$
• Is there any hidden symmetry in the stripe structure of perovskite high temperature superconductors?
• Pressure-dependent structure of BaZrO${}_3$ crystals as determined by Raman Spectroscopy
• Stability of the tetragonal phase of BaZrO3 under high pressure
• Evidence for pressure induced polarization rotation, octahedral tilting and reentrant ferroelectric phase in tetragonal (Pb0.5Bi0.5)(Ti0.5Fe0.5)O3
• Synergistic effects of rare-earth doping on the magnetic properties of orthochromates: A machine learning approach
• Anomalous pressure dependence of the electronic transport and anisotropy in SrIrO3 films
• Unraveling structural, electronic, and magnetic ambiguities in Pb1-δCrO3 with an insulating charge-transfer band structure
• Sub-unit cell engineering of CrVO${}_3$ superlattice thin films