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oai:figshare.com:article/34050189 2026-10-01T18:11:10Z category_1 category_915 category_7 category_12 category_16 category_21 category_873 category_734 portal_63 item_type_6 month_year_10_2026

Evidencing Prominent Involvement of Bi Orbitals of BiFeO₃ in Eliciting Charge-Transfer Excitation Syeda Reha Khadri (25158174) Florian Schrenk (25158177) Ryoma Suzuki (5342069) Jonathan Rollenitz (25158180) Shunsuke Yuyama (11831854) Akihiro Furube (537083) Christoph Rameshan (1377459) Dharmapura H. K. Murthy (3614735) Biophysics Physical Sciences not elsewhere classified Medicine Cell Biology Physiology Biotechnology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified ray photoelectron spectroscopy distinctive decay behavior comprehensive correlation evidences chemical bonding perspective generation multifunctional applications evidencing prominent involvement fe 3d orbitals 3 </ sub bi 6p orbitals cb states compared eliciting ct excitation transfer excitation bifeo bi orbitals valence states significant involvement finds applications orbitals involved ct excitation eliciting charge using near results aid optoelectronic properties occur due gap defects first time energy conversion electronic properties electron transitions conduction band completely disregarding cb ), ambient x BiFeO₃ (BFO) finds applications in spintronics, multiferroics, sensors, piezoelectricity, emerging ferroelectric solar cells, and photocatalysis. However, the performance of BFO depends on its electronic properties and charge-transfer (CT) excitation, which are governed by the extent/choice of orbitals involved in hybridization. The CT excitation is often assumed to occur due to electron transitions from the O 2p to Fe 3d orbitals of the conduction band (CB), while completely disregarding the role of Bi 6p orbitals. For the first time, using near-ambient x-ray photoelectron spectroscopy under light illumination, valence states of BFO constituents are deconvoluted. By selectively probing different orbitals of the CB under illumination, the often-ignored role of Bi orbitals in CT excitation is rationalized. In addition, ultrafast transient absorption spectroscopy unravels the distinctive decay behavior of charge carriers in CB states compared with that in in-gap defects. Such comprehensive correlation evidences on the significant involvement of Bi orbitals in eliciting CT excitation from a chemical bonding perspective. Results aid in establishing missing links among band structure, optoelectronic properties, and function/performance of BFO. Such insights are key to improving the performance of next-generation multifunctional applications of BFO, particularly in solar-energy conversion. 2026-10-01T00:00:00Z Text Journal contribution 10.1021/acsphyschemau.6c00108.s001 https://figshare.com/articles/journal_contribution/Evidencing_Prominent_Involvement_of_Bi_Orbitals_of_BiFeO_sub_3_sub_in_Eliciting_Charge-Transfer_Excitation/34050189 CC BY-NC 4.0