Identification of electronic state in perovskiteCaCrO3by high-pressure studies

J.-S. Zhou, J. A. Alonso, J. Sanchez-Benitez, M. T. Fernandez-Diaz, R. Martinez-Coronado, L.-P. Cao, X. Li, L. G. Marshall, C.-Q. Jin, J. B. Goodenough
2015 Physical Review B  
CaCrO 3 is at the crossover from localized to itinerant electronic behavior, and interpretation of its electronic state has remained controversial. It is a metal from an optical study. However, the collinear type-C antiferromagnetic spin ordering below T N ≈ 90 K is characteristic of localized electron magnetism. We have performed many runs of high-pressure synthesis. CaCrO 3 crystals can be found in some batches. We have used specific-heat measurement as a diagnostic tool to probe the
more » ... c states near the Fermi energy. An electronic bandwidth is broadened by applying high pressure. The magnetization measurement under pressure reveals a dT N /dP < 0. The crystal structural change corresponding to the pressure-induced electron structural change has been monitored by in-situ neutron diffraction under high pressure. The d-electron configuration on octahedral site Cr 4+ is orbitally threefold degenerate. Local site distortions are argued to show that in CaCrO 3 the crossover from localized to itinerant 3d electrons does not result in a charge-density wave in which segregation of the interatomic interactions results in the stabilization of molecular clusters, but in an intraatomic orbital ordering that stabilizes a halffilled localized-electron xy orbital and a ¼-filled c-axis π* band. Local structural changes under pressure reveal a weakening of long-range magnetic order is associated with a smooth Mott-Hubbard transition of the xy electrons.
doi:10.1103/physrevb.92.144421 fatcat:q3aucg65vfcbpmkwo7nusj7uf4