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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c7sc00830a· OSTI ID:1506235
 [1];  [2];  [2];  [3];  [3];  [3];  [3];  [3];  [2];  [3]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Physics
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
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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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-08ER46521; SC0001088
OSTI ID:
1506235
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 11 Vol. 8; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

A Trigonal Prismatic Cobalt(II) Complex as a Single Molecule Magnet with a Reduced Contribution from Quantum Tunneling journal March 2019
Ultra-broadband EPR spectroscopy in field and frequency domains journal January 2018
A new series of tetrahedral Co( ii ) complexes [CoLX 2 ] (X = NCS, Cl, Br, I) manifesting single-ion magnet features journal January 2018

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