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Title: Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals

Abstract

We carry out x-ray absorption spectroscopy experiment at the oxygen K edge in croconic acid (C5H2O5) crystal as a prototype of ferroelectric organic molecular solid, whose electric polarization is generated by proton transfer. The experimental spectrum is well reproduced by the electron-hole excitation theory simulations from configuration generated by ab initio molecular dynamics simulation. When inversion symmetry is broken in the ferroelectric state, the hydrogen bonding environment on the two bonded molecules become inequivalent. Such a difference is sensitively probed by the bound excitation in the pre-edge, which is strongly localized on the excited molecules. Our analysis shows that a satellite peak in the pre-edge will emerge at higher excitation energy, which serves as a clear signature of ferroelectricity in the material.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of Nebraska, Lincoln, NE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), High Energy Physics (HEP); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Advanced Light Source, Lawrence Berkeley National Lab
OSTI Identifier:
1603274
Alternate Identifier(s):
OSTI ID: 1602371; OSTI ID: 1632137; OSTI ID: 1656945
Report Number(s):
BNL-213692-2020-JAAM
Journal ID: ISSN 2475-9953; PRMHAR; TRN: US2104677
Grant/Contract Number:  
SC0019173; AC02-05CH11231; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Electronic structure of atoms & molecules; Ferroelectrics; X-ray absorption near-edge spectroscopy

Citation Formats

Tang, Fujie, Jiang, Xuanyuan, Ko, Hsin-Yu, Xu, Jianhang, Topsakal, Mehmet, Hao, Guanhua, N'Diaye, Alpha T., Dowben, Peter A., Lu, Deyu, Xu, Xiaoshan, and Wu, Xifan. Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals. United States: N. p., 2020. Web. doi:10.1103/PhysRevMaterials.4.034401.
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Tang, Fujie, Jiang, Xuanyuan, Ko, Hsin-Yu, Xu, Jianhang, Topsakal, Mehmet, Hao, Guanhua, N'Diaye, Alpha T., Dowben, Peter A., Lu, Deyu, Xu, Xiaoshan, & Wu, Xifan. Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals. United States. https://doi.org/10.1103/PhysRevMaterials.4.034401
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Tang, Fujie, Jiang, Xuanyuan, Ko, Hsin-Yu, Xu, Jianhang, Topsakal, Mehmet, Hao, Guanhua, N'Diaye, Alpha T., Dowben, Peter A., Lu, Deyu, Xu, Xiaoshan, and Wu, Xifan. Mon . "Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals". United States. https://doi.org/10.1103/PhysRevMaterials.4.034401. https://www.osti.gov/servlets/purl/1603274.
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@article{osti_1603274,
title = {Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals},
author = {Tang, Fujie and Jiang, Xuanyuan and Ko, Hsin-Yu and Xu, Jianhang and Topsakal, Mehmet and Hao, Guanhua and N'Diaye, Alpha T. and Dowben, Peter A. and Lu, Deyu and Xu, Xiaoshan and Wu, Xifan},
abstractNote = {We carry out x-ray absorption spectroscopy experiment at the oxygen K edge in croconic acid (C5H2O5) crystal as a prototype of ferroelectric organic molecular solid, whose electric polarization is generated by proton transfer. The experimental spectrum is well reproduced by the electron-hole excitation theory simulations from configuration generated by ab initio molecular dynamics simulation. When inversion symmetry is broken in the ferroelectric state, the hydrogen bonding environment on the two bonded molecules become inequivalent. Such a difference is sensitively probed by the bound excitation in the pre-edge, which is strongly localized on the excited molecules. Our analysis shows that a satellite peak in the pre-edge will emerge at higher excitation energy, which serves as a clear signature of ferroelectricity in the material.},
doi = {10.1103/PhysRevMaterials.4.034401},
journal = {Physical Review Materials},
number = 3,
volume = 4,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2020},
month = {Mon Mar 02 00:00:00 EST 2020}
}
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https://doi.org/10.1103/PhysRevMaterials.4.034401
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