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Title: Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy

Abstract

Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science.

Authors:
ORCiD logo [1];  [2];  [2];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Physics
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1506235
Grant/Contract Number:  
FG02-08ER46521; SC0001088
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lu, Jian, Ozel, I. Ozge, Belvin, Carina A., Li, Xian, Skorupskii, Grigorii, Sun, Lei, Ofori-Okai, Benjamin K., Dincă, Mircea, Gedik, Nuh, and Nelson, Keith A. Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy. United States: N. p., 2017. Web. doi:10.1039/c7sc00830a.
Lu, Jian, Ozel, I. Ozge, Belvin, Carina A., Li, Xian, Skorupskii, Grigorii, Sun, Lei, Ofori-Okai, Benjamin K., Dincă, Mircea, Gedik, Nuh, & Nelson, Keith A. Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy. United States. doi:10.1039/c7sc00830a.
Lu, Jian, Ozel, I. Ozge, Belvin, Carina A., Li, Xian, Skorupskii, Grigorii, Sun, Lei, Ofori-Okai, Benjamin K., Dincă, Mircea, Gedik, Nuh, and Nelson, Keith A. Wed . "Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy". United States. doi:10.1039/c7sc00830a. https://www.osti.gov/servlets/purl/1506235.
@article{osti_1506235,
title = {Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy},
author = {Lu, Jian and Ozel, I. Ozge and Belvin, Carina A. and Li, Xian and Skorupskii, Grigorii and Sun, Lei and Ofori-Okai, Benjamin K. and Dincă, Mircea and Gedik, Nuh and Nelson, Keith A.},
abstractNote = {Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science.},
doi = {10.1039/c7sc00830a},
journal = {Chemical Science},
number = 11,
volume = 8,
place = {United States},
year = {2017},
month = {4}
}

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