UWB DEER and RIDME distance measurements in Cu(II)-Cu(II) spin pairs

Journal of Magnetic Resonance
Frauke D BreitgoffGunnar Jeschke

Abstract

Distance determination by Electron Paramagnetic Resonance (EPR) based on measurements of the dipolar coupling are technically challenging for electron spin systems with broad spectra due to comparatively narrow microwave pulse excitation bandwidths. With Na4[{CuII(PyMTA)}-(stiff spacer)-{CuII(PyMTA)}] as a model compound, we compared DEER and RIDME measurements and investigated the use of frequency-swept pulses. We found very large improvements in sensitivity when substituting the monochromatic pump pulse by a frequency-swept one in DEER experiments with monochromatic observer pulses. This effect was especially strong in X band, where nearly the whole spectrum can be included in the experiment. The RIDME experiment is characterised by a trade-off in signal intensity and modulation depth. Optimal parameters are further influenced by varying steepness of the background decay. A simple 2-point optimization experiment was found to serve as good estimate to identify the mixing time of highest sensitivity. Using frequency-swept pulses in the observer sequences resulted in lower SNR in both the RIDME and the DEER experiment. Orientation selectivity was found to vary in both experiments with the detection position as well as with the s...Continue Reading

Citations

Sep 25, 2020·Physical Chemistry Chemical Physics : PCCP·K KellerG Jeschke
Dec 3, 2020·Journal of Magnetic Resonance·Mantas ŠimėnasJohn J L Morton
Mar 10, 2021·The Journal of Chemical Physics·Jean-Baptiste VerstraeteMohammadali Foroozandeh
Jan 22, 2021·Accounts of Chemical Research·Austin Gamble JarviSunil Saxena
May 13, 2021·The Journal of Physical Chemistry Letters·Joshua CastoSunil Saxena
May 18, 2021·The Journal of Physical Chemistry. B·Katrin AckermannBela E Bode

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