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Sequential Spin State Transition and Intermetallic Charge Transfer in PbCoO3

MPG-Autoren
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Agrestini,  Stefano
Stefano Agrestini, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Chen,  Kai
Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Liao,  Sheng-Chieh
Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Hu,  Zhiwei
Zhiwei Hu, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Zitation

Liu, Z., Sakai, Y., Yang, J., Li, W., Liu, Y., Ye, X., et al. (2020). Sequential Spin State Transition and Intermetallic Charge Transfer in PbCoO3. Journal of the American Chemical Society, 142, 5731-5741. doi:10.1021/jacs.9b13508.


Zitierlink: https://hdl.handle.net/21.11116/0000-0006-09EA-9
Zusammenfassung
Spin state transitions and intermetallic charge transfers can essentially change material structural and physical properties while excluding external chemical doping. However, these two effects have rarely been found to occur sequentially in a specific material. In this article, we show the realization of these two phenomena in a perovskite oxide PbCoO3 with a simple ABO3 composition under high pressure. PbCoO3 possesses a peculiar A- and B-site ordered charge distribution Pb2+Pb4+3Co2+2Co3+2O12 with insulating behavior at ambient conditions. The high spin Co2+ gradually changes to low spin with increasing pressure up to about 15 GPa, leading to an anomalous increase of resistance magnitude. Between 15 and 30 GPa, the intermetallic charge transfer occurs between Pb4+ and Co2+ cations. The accumulated charge-transfer effect triggers a metal-insulator transition as well as a first-order structural phase transition toward a Tetra.-I phase at the onset of ∼20 GPa near room temperature. On further compression over 30 GPa, the charge transfer completes, giving rise to another first-order structural transformation toward a Tetra.-II phase and the reentrant electrical insulating behavior.