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Ab Initio Prediction of Excited-State and Polaron Effects in Transient XUV Measurements of α-Fe₂O₃

Klein, Isabel M. and Liu, Hanzhe and Nimlos, Danika and Krotz, Alex and Cushing, Scott Kevin (2022) Ab Initio Prediction of Excited-State and Polaron Effects in Transient XUV Measurements of α-Fe₂O₃. Journal of the American Chemical Society, 144 (28). pp. 12834-12841. ISSN 0002-7863. doi:10.1021/jacs.2c03994.

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Transient X-ray and extreme ultraviolet (XUV) spectroscopies have become invaluable tools for studying photoexcited dynamics due to their sensitivity to carrier occupations and local chemical or structural changes. One of the most studied materials using transient XUV spectroscopy is α-Fe₂O₃ because of its rich photoexcited dynamics, including small polaron formation. The interpretation of carrier and polaron effects in α-Fe₂O₃ is currently carried out using a semi-empirical method that is not transferrable to most materials. Here, an ab initio, Bethe-Salpeter equation (BSE) approach is developed that can incorporate photoexcited-state effects into arbitrary material systems. The accuracy of this approach is proven by calculating the XUV absorption spectra for the ground, photoexcited, and polaron states of α-Fe₂O₃. Furthermore, the theoretical approach allows for the projection of the core-valence excitons and different components of the X-ray transition Hamiltonian onto the band structure, providing new insights into old measurements. From this information, a physical intuition about the origins and nature of the transient XUV spectra can be built. A route to extracting electron and hole energies is even shown possible for highly angular momentum split XUV peaks. This method is easily generalized to K, L, M, and N edges to provide a general approach for analyzing transient X-ray absorption or reflection data.

Item Type:Article
Related URLs:
URLURL TypeDescription
Klein, Isabel M.0000-0001-6134-6732
Liu, Hanzhe0000-0001-9001-725X
Nimlos, Danika0000-0002-5414-0039
Krotz, Alex0000-0001-8189-7902
Cushing, Scott Kevin0000-0003-3538-2259
Additional Information:© 2022 American Chemical Society. Received: April 13, 2022; Published: July 11, 2022. I.M.K. was supported by an NSF Graduate Research Fellowship (DGE-1745301). H.L. and D.N. were supported by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. Author Contributions. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest.
Group:Liquid Sunlight Alliance
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1745301
Department of Energy (DOE)DE-SC0021266
Subject Keywords:Absorption spectroscopy, Band structure, Hamiltonians, Polarons, X-rays
Issue or Number:28
Record Number:CaltechAUTHORS:20220712-372197000
Persistent URL:
Official Citation:Ab Initio Prediction of Excited-State and Polaron Effects in Transient XUV Measurements of α-Fe2O3. Isabel M. Klein, Hanzhe Liu, Danika Nimlos, Alex Krotz, and Scott Kevin Cushing. Journal of the American Chemical Society 2022 144 (28), 12834-12841; DOI: 10.1021/jacs.2c03994
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:115494
Deposited By: George Porter
Deposited On:13 Jul 2022 19:26
Last Modified:02 Aug 2022 20:42

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