5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems

In 3-pulse ESEEM and the original 4-pulse HYSCORE, nuclei with large modulation depth ( k ≈ 1) suppress spectral peaks from nuclei with weak modulations ( k ≈ 0). This cross suppression can impede the detection of the latter nuclei, which are often the ones of interest. We show that two extended pulse sequences, 5-pulse ESEEM and 6-pulse HYSCORE, can be used as experimental alternatives that suffer less strongly from the cross suppression and allow to recover signals of k ≈ 0 nuclei in the presence of k ≈ 1 nuclei. In the extended sequences, modulations from k ≈ 0 nuclei are strongly enhanced. In addition, multi-quantum transitions are absent which simplifies the spectra. General analytical expressions for the modulation signals in these sequences are derived and discussed. Numerical simulations and experimental spectra that demonstrate the higher sensitivity of the extended pulse sequences are presented.