Dynamic Competition between Hubbard and Superexchange Interactions Selectively Localizes Electrons and Holes through Polarons

Mendes, Jocelyn L.; Shin, Hyun Jun; Seo, Jae Yeon; Lee, Nara; Choi, Young Jai; Varley, Joel B.; Cushing, Scott K.

doi:10.1021/jacs.4c16837

Dynamic Competition between Hubbard and Superexchange Interactions Selectively Localizes Electrons and Holes through Polarons

Journal Article · Fri May 02 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c16837· OSTI ID:2575663

Mendes, Jocelyn L. ^[1]; Shin, Hyun Jun ^[2]; Seo, Jae Yeon ^[2]; Lee, Nara ^[2]; Choi, Young Jai ^[2]; ^[3]; Cushing, Scott K. ^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States)
Yonsei Univ., Seoul (Korea, Republic of)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Controlling the effects of photoexcited polarons in transition metal oxides can enable the long time-scale charge separation necessary for renewable energy applications and controlling new quantum phases through dynamically tunable electron–phonon coupling. In previously studied transition metal oxides, polaron formation is facilitated by a photoexcited ligand-to-metal charge transfer (LMCT). When the polaron is formed, oxygen atoms move away from iron centers, which increases carrier localization at the metal center and decreases charge hopping. Studies of yttrium iron garnet and erbium iron oxide have suggested that strong electron and spin correlations can modulate photoexcited polaron formation. To understand the interplay between strong spin and electronic correlations in highly polar materials, we studied gadolinium iron oxide (GdFeO₃), which selectively forms photoexcited polarons through an Fe–O–Fe superexchange interaction. Excitation-wavelength-dependent transient extreme ultraviolet (XUV) spectroscopy selectively excites LMCT and metal-to-metal charge transfer (MMCT) transitions. Here, the LMCT transition suppresses photoexcited polaron formation due to the balance between superexchange and Hubbard interactions, while MMCT transitions result in photoexcited polaron formation within 250 ± 40 fs. Ab initio theory demonstrates that electron and hole polarons localize on iron centers following MMCT. In addition to understanding how strong electronic and spin correlations can control strong electron–phonon coupling, these experiments separately measure electron and hole polaron interactions on neighboring metal centers for the first time, providing insight into a large range of charge-transfer and Mott–Hubbard insulators.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); National Research Foundation of Korea (NRF); National Energy Research Scientific Computing Center (NERSC); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344; SC0021266; AC02-05CH11231

OSTI ID:: 2575663

Report Number(s):: LLNL--JRNL-871244

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 19 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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