Journal article
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites, from O K-edge X-ray Absorption Spectroscopy
Journal of physical chemistry. C, v 118(4), pp 1856-1863
30 Jan 2014
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Abstract
The interaction between the transition metal 3d and the oxygen 2p states via hybridization underpins many of the phenomena in transition metal oxide materials. We report the empirical trend of this interaction using the pre-edge feature of the 0 Kedge X-ray absorption spectrum. Our assessment method is built on the dipole approximation and the configuration interaction between the transition metal 3d and the oxygen 2p states. We found that hybridization increases with the number of 3d electrons, consistent with the expected electronegativity trend. We support this analysis with density functional calculations, which reveal a systematic increase in the transition metal 3d and the oxygen 2p state mixing with increasing 3d-electron number. Oxidation of the transition metal was also found to increase hybridization, which we believe reflects the reduced transition metal 3d and oxygen 2p energy difference, causing increased covalency. We compare the analysis from the surface-sensitive electron-yield and the bulk-sensitive fluorescence-yield spectra, revealing that either method can be used to study the hybridization trend. We finally compare and discuss the influence of the lanthanide ions and the influence of the covalency on oxygen electrocatalysis. Our study describes an efficient and simple approach to understand the hybridization trend in transition metal oxides, which has considerable implications for electrochemical energy conversion processes.
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Details
- Title
- Estimating Hybridization of Transition Metal and Oxygen States in Perovskites, from O K-edge X-ray Absorption Spectroscopy
- Creators
- Jin Suntivich - Massachusetts Institute of TechnologyWesley T. Hong - Massachusetts Institute of TechnologyYueh-Lin Lee - Massachusetts Institute of TechnologyJames M. Rondinelli - Drexel UniversityWanli Yang - Lawrence Berkeley National LaboratoryJohn B. Goodenough - The University of Texas at AustinBogdan Dabrowski - Northern Illinois UniversityJohn W. Freeland - Argonne National LaboratoryYang Shao-Horn - Massachusetts Institute of Technology
- Publication Details
- Journal of physical chemistry. C, v 118(4), pp 1856-1863
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 8
- Grant note
- DE-FG02-05ER15728 / DOE Hydrogen Initiative Program; United States Department of Energy (DOE) Ziff Environmental Fellowship (Harvard) DE-AC02-05CH11231 / Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy; United States Department of Energy (DOE) Robert A. Welch Foundation, Houston, TX; The Welch Foundation DE-AC02-06CH11357 / U.S. Department of Energy, Office of Basic Energy Sciences; United States Department of Energy (DOE) Chesonis Foundation Fellowship (MIT) SISGR DE-SC0002633 / DOE Basic Energy Science; United States Department of Energy (DOE) Toyota Motor Company W911NF-12-1-0133 / ARO
- Resource Type
- Journal article
- Language
- English
- Web of Science ID
- WOS:000330610200012
- Scopus ID
- 2-s2.0-84893212875
- Other Identifier
- 991019330913404721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Physical
- Materials Science, Multidisciplinary
- Nanoscience & Nanotechnology