Abstract
Electron-nuclear double resonance (ENDOR) is a method of choice to detect magnetic nuclei in the coordination sphere of paramagnetic molecules, but its sensitivity substantially suffers from saturation effects. Recently we introduced a new pulsed ENDOR experiment based on electron-nuclear cross polarisation (CP) transfer. Here we analyse the time evolution of the spin polarization in CP-ENDOR and show that CP combined with inherent fast relaxation leads to enhanced sensitivity as compared to Davies ENDOR.
Highlights
Electron-nuclear double resonance (ENDOR) is a method of choice to detect magnetic nuclei in the coordination sphere of paramagnetic molecules, but its sensitivity substantially suffers from saturation effects
To assign the fitted rate values, the electron spin-lattice relaxation time was determined by inversion recovery experiments§ and the nuclear spin-lattice relaxation time T1I of the ENDOR lines at DoEnNDOR = Æ2.5 MHz was estimated by monitoring the signal intensity of Davies ENDOR-spectra as a function of the shot repetition time (SI), as proposed by Tyryshkin et al.[14]
We have demonstrated that the cross polarisation (CP) ENDOR experiment can be carried out using a repetition time on the order of the electron spin relaxation time in contrast to standard Davies ENDOR, which requires waiting times on the order of the nuclear spin lattice relaxation
Summary
Electron-nuclear double resonance (ENDOR) is a method of choice to detect magnetic nuclei in the coordination sphere of paramagnetic molecules, but its sensitivity substantially suffers from saturation effects. We analyse the time evolution of the spin polarization in CP-ENDOR and show that CP combined with inherent fast relaxation leads to enhanced sensitivity as compared to Davies ENDOR.
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