Anomalous high-pressure Jahn-Teller behavior in CuWO4
J Ruiz-Fuertes1, A Segura, F Rodríguez
1Departamento de Física Aplicada-ICMUV, Universitat de València, Edificio de Investigación, c/ Dr. Moliner 50, 46100 Burjassot, Valencia, Spain. javier.ruiz-fuertes@uv.es
Abstract:
High-pressure optical-absorption measurements performed in CuWO(4) up to 20 GPa provide experimental evidence of the persistence of the Jahn-Teller (JT) distortion in the whole pressure range both in the low-pressure triclinic and in the high-pressure monoclinic phase. The electron-lattice couplings associated with the e(g)(E⊗e) and t(2g)(T⊗e) orbitals of Cu(2+) in CuWO(4) are obtained from correlations between the JT distortion of the CuO(6) octahedron and the associated structure of Cu(2+) d-electronic levels. This distortion and its associated JT energy (E(JT)) decrease upon compression in both phases. However, both the distortion and associated E(JT) increase sharply at the phase-transition pressure (P(PT)=9.9 GPa), and we estimate that the JT distortion persists for a wide pressure range not being suppressed up to 37 GPa. These results shed light on the transition mechanism of multiferroic CuWO(4), suggesting that the pressure-induced structural phase transition is a way to minimize the distortive effects associated with the toughness of the JT distortion.
Related Concept Videos
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
01:26Imperfections in Crystal Structure: Stoichiometric Point Defects
01:29Imperfections in Crystal Structure: Non-Stoichiometric Defects
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
01:29Crystallographic Point Groups