On the role of electron–nucleus contact and microwave saturation in thermal mixing DNP

Abstract

We have explored the manifold physical scenarios emerging from a model of Dynamic Nuclear Polarization (DNP) via thermal mixing under the hypothesis of highly effective electron-electron interaction. When the electron and nuclear reservoirs are also assumed to be in strong thermal contact and the microwave irradiation saturates the target electron transition, the enhancement of the nuclear polarization is expected to be considerably high even if the irradiation frequency is set far away from the centre of the ESR line (as already predicted by Borghini) and the typical polarization time is reduced on moving towards the boundaries of the said line. More reasonable behaviours are obtained by reducing the level of microwave saturation or the contact between electrons and nuclei in the presence of nuclear leakage. In both cases the function describing the dependency of the steady state nuclear polarization on the frequency of irradiation becomes sharper at the edges and the build up rate decreases on moving off-resonance. Although qualitatively similar in terms of the effects produced on nuclear polarization, the degree of microwave saturation and of electron-nucleus contact has a totally different impact on electron polarization, which is of course strongly correlated to the effectiveness of saturation and almost insensitive, at the steady state, to the magnitude of the interactions between the two spin reservoirs. The likelihood of different scenarios is discussed in the light of the experimental data currently available in the literature, to point out which aspects are suitably accounted for and which are not by the declination of thermal mixing DNP considered here.