Journal
NANO LETTERS
Volume 21, Issue 19, Pages 8433-8438Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.1c03103
Keywords
charge disproportionation; X-ray spectroscopy; density functional theory; thin films; molecular orbital theory
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Funding
- DST-SERB [CRG/2019/001627]
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This study investigates the mechanism of charge disproportionation in BaBiO3, finding that different hybridizations lead to different oxidation states in the material, validated through a combination of X-ray spectroscopic experiments and first-principle calculations. Additionally, the nature of charge disproportionation varies at room temperature and 200K.
BaBiO3(BBO) is known to be a valence-skipping perovskite, which avoids the metallic state through charge disproportionation (CD), the mechanism of which is still unresolved. A novel mechanism for CD is presented here in the covalent limit using a molecular orbital (MO) picture under two scenarios: (case i) Bi 6sp-O 2p and (case ii) Bi 6p-O 2p hybridizations that favor 5+ and 3+ states, respectively. The proposed model is further validated by using a combinatorial approach of X-ray spectroscopic experiments and first-principle calculations. The bulk X-ray photoemission spectrum reveals that, at room temperature, the CD is dynamic in nature, whereas, at 200 K, it approaches a quasi-static limit. Under compressive strain, the octahedral breathing mode is damped and drives the system to a quasi-static limit even at room temperature, giving rise to asymmetric CD.
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