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EPR Spectroscopy: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Contributor: Jack Zhong

EPR spectroscopy is a magnetic resonance technique that detects species carrying one or more unpaired electrons: organic radicals, transition-metal ions and point defects in solids. The sample is placed in a static magnetic field and irradiated at microwave frequency; the electron spin is excited when the field and the frequency meet the resonance condition, and the g value, the hyperfine splitting from neighbouring nuclei and the zero-field splitting report on the electronic structure and on the environment of the spin [1]. Sensitivity is high compared with nuclear magnetic resonance, and because only paramagnetic centres are visible the method is selective for radicals embedded in a diamagnetic matrix [2]. Continuous-wave instruments record the absorption while the field is swept, whereas pulsed experiments separate the interactions in time; double electron-electron resonance measures the dipolar coupling between two spins and so gives distances of roughly 1.5 to 8 nanometres, a range that has been used to follow conformational change in proteins [3], and a distance distribution can still be recovered when the zero-field splitting is large [4]. Assigning a spectrum generally requires simulating it, and g tensors and hyperfine couplings are now also obtained from first-principles calculation [5].

  • electron paramagnetic resonance
  • unpaired electron
  • hyperfine coupling
  • spin label
  • pulsed EPR
  • double electron-electron resonance

References

  1. Hegde, B.G.; Electron paramagnetic resonance spectroscopy. Resonance 2015, 20, 1017-1032, 10.1007/s12045-015-0270-8.
  2. Klare, J.P.; Biomedical applications of electron paramagnetic resonance (EPR) spectroscopy. Biomedical Spectroscopy and Imaging 2012, 1, 101-124, 10.3233/bsi-2012-0010.
  3. van Amsterdam, I.M.C.; Ubbink, M.; Canters, G.W.; Huber, M.; Measurement of a Cu-Cu Distance of 26 Angstrom by a Pulsed EPR Method. Angewandte Chemie International Edition 2003, 42, 62-64, 10.1002/anie.200390053.
  4. Misra, S.K.; Salahi, H.R.; Estimation of Distance Distributions Between Gd3+ Ion Pairs with a Significant Zero-Field Splitting from Pulsed EPR DEER Data. Applied Magnetic Resonance 2023, 54, 383-400, 10.1007/s00723-022-01521-8.
  5. Kadantsev, E.S.; Ziegler, T.; First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids. Magnetic Resonance in Chemistry 2010, 48, S2-S10, 10.1002/mrc.2655.
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