Abstract
ELDOR-detected NMR (EDNMR) performed at higher magnetic fields is becoming an increasingly popular alternative to conventional ENDOR for the characterization of electron-nuclear hyperfine interactions owing to its enhanced sensitivity. However there are two key problems that limit its widespread adoption, with factors controlling: (i) lineshape distortions and; (ii) overall spectral resolution, still largely understood only at a qualitative level. Indeed highly anisotropic (dipolar) coupled species are particularly problematic in the EDNMR experiment. Nor is it clear as to whether line intensities measured in EDNMR can provide quantitative information. Here we describe how all these problems can be overcome for a nitroxide radical as model system. We introduce a simulation procedure/protocol for the simulation of EDNMR line-shapes collected over a range of high turning angle (HTA) pulse lengths. It is shown that spectral line-shapes can be robustly reproduced and that the intensities of spectral lines and the spin nutation behavior can be quantitatively assessed. This broadens the scope of the EDNMR experiment as a generally applicable, quantitative double resonance method.
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