Title

Resonant photoemission of single-crystal RBaCo2O 5+δ (R=Gd, Dy)

Document Type

Article

Publication Date

1-1-2004

Abstract

Resonant photoemission of single crystals of the double perovskites GdBaCo2O5+δ and DyBaCo2O 5+δ has been carried out at the UK Synchrotron Radiation Source at Daresbury. The resonance onset energy at the Co 3p→3d threshold is used to explore the Co spin state in the double perovskites as a function of temperature. In contrast with the simple perovskites LaCoO3 and HoCoO3, an undelayed resonance is observed for GdBaCo 2O5+δ and DyBaCo2O5+δ at temperatures as low as 50 K, consistent with the idea that the Co spin state in the pyramidal sites of the double perovskites does not fluctuate with temperature. The temperature variation of the data suggest that the phase transition observed in GdBaCo2O5+δ at around 350 K is not associated with a sudden low spin-high spin switch in the octahedral sites. The giant rare earth (R) 4d→4f resonances are also probed, and are used to identify the 4f contributions to the valence band. This shows that the density of states close to the Fermi energy for all materials is of Co 3d/O 2p character, with no R 4f contribution. Comparison is made with LSDA + U calculations. Our experiments indicate that the spin equilibrium in the double perovskites is significantly shifted in favor of higher spin multiplicities compared with materials such as LaCoO3.

Publication Source (Journal or Book title)

Physical Review B - Condensed Matter and Materials Physics

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