Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy
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Author(s)
Lu, Jian
Ozel, Ilkem Ozge
Belvin, Carina Aiello
Li, Xian
Skorupskii, Grigorii
Sun, Lei
Ofori-Okai, Benjamin Kwasi
Dinca, Mircea
Gedik, Nuh
Nelson, Keith Adam
Date Issued
April 2017
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Lu, Jian, et al. “Rapid and Precise Determination of Zero-Field Splittings by Terahertz Time-Domain Electron Paramagnetic Resonance Spectroscopy.” Chem. Sci. 8, 11 (April 2017): 7312–7323 © 2017 The Royal Society of Chemistry.
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Final published version
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology. Department of Physics
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DOI of Published Version
https://doi.org/10.1039/C7SC00830A
