Articles | Volume 6, issue 1
https://doi.org/10.5194/mr-6-33-2025
https://doi.org/10.5194/mr-6-33-2025
Research article
 | 
24 Jan 2025
Research article |  | 24 Jan 2025

Increased sensitivity in electron–nuclear double resonance spectroscopy with chirped radiofrequency pulses

Julian Stropp, Nino Wili, Niels C. Nielsen, and Daniel Klose

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Cited articles

Abragam, A.: The Principles of Nuclear Magnetism, Oxford University Press, ISBN 9780198520146, 1961. a
Allouche, F., Klose, D., Gordon, C. P., Ashuiev, A., Wörle, M., Kalendra, V., Mougel, V., Copéret, C., and Jeschke, G.: Low‐Coordinated Titanium(III) Alkyl–Molecular and Surface–Complexes: Detailed Structure from Advanced EPR Spectroscopy, Angew. Chem., 130, 14741–14745, https://doi.org/10.1002/ange.201806497, 2018. a
Ashuiev, A., Allouche, F., Wili, N., Searles, K., Klose, D., Copéret, C., and Jeschke, G.: Molecular and supported Ti(III)-alkyls: efficient ethylene polymerization driven by the π-character of metal–carbon bonds and back donation from a singly occupied molecular orbital, Chemical Science, 12, 780–792, https://doi.org/10.1039/d0sc04436a, 2021. a
Baum, J., Tycko, R., and Pines, A.: Broadband and adiabatic inversion of a two-level system by phase-modulated pulses, Phys. Rev. A, 32, 3435–3447, https://doi.org/10.1103/physreva.32.3435, 1985. a, b
Biehl, R., Plato, M., and Möbius, K.: General TRIPLE resonance on free radicals in solution. Determination of relative signs of isotropic hyperfine coupling constants, J. Chem. Phys., 63, 3515–3522, https://doi.org/10.1063/1.431790, 1975. a
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Short summary
Sensitivity is often a limiting factor in electron–nuclear double resonance (ENDOR). Here we demonstrate how using chirp radiofrequency pulses can improve ENDOR sensitivity up to 3–9 fold, with the strongest increase for broader lines often encountered in disordered solids for nuclei such as nitrogen and metals. The resulting drastic speedup in acquisition times also renders 2D ENDOR more feasible, as we demonstrate in TRIPLE, showing correlations with Cu hyperfine couplings.