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Large Charge‐Transfer Energy in LiFePO 4 Revealed by Full‐Multiplet Calculation for the Fe L 3 ‐edge Soft X‐ray Emission Spectra
Author(s) -
Asakura Daisuke,
Nanba Yusuke,
Makinose Yuki,
Matsuda Hirofumi,
Glans PerAnders,
Guo Jinghua,
Hosono Eiji
Publication year - 2018
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800038
Subject(s) - multiplet , spectral line , emission spectrum , electronic structure , k edge , spectroscopy , charge (physics) , chemistry , electron transfer , atomic physics , materials science , analytical chemistry (journal) , computational chemistry , physics , chromatography , quantum mechanics , astronomy
We analyzed the Fe 3d electronic structure in LiFePO 4 /FePO 4 (LFP/FP) nanowire with a high cyclability by using soft X‐ray emission spectroscopy (XES) combined with configuration‐interaction full‐multiplet (CIFM) calculation. The ex situ Fe L 2,3 ‐edge resonant XES (RXES) spectra for LFP and FP are ascribed to oxidation states of Fe 2+ and Fe 3+ , respectively. CIFM calculations for Fe 2+ and Fe 3+ states reproduced the Fe L 3 RXES spectra for LFP and FP, respectively. In the calculations for both states, the charge‐transfer energy was considerably larger than those for typical iron oxides, indicating very little electron transfer from the O 2p to Fe 3d orbitals and a weak hybridization on the Fe−O bond during the charge–discharge reactions.