On the role of electron-nucleus contact and microwave saturation in Thermal Mixing DNP

TL;DR

This paper models the effects of electron-nucleus contact and microwave saturation on thermal mixing DNP, revealing how these factors influence nuclear and electron polarization behaviors under various conditions.

Contribution

It provides a detailed theoretical analysis of how microwave saturation and electron-nucleus contact affect polarization in thermal mixing DNP, incorporating experimental data comparisons.

Findings

High nuclear polarization enhancement possible with strong electron-electron interaction and microwave saturation.

Reducing microwave saturation or electron-nucleus contact sharpens the polarization frequency dependence.

Electron polarization is less affected by these parameters at steady state.

Abstract

We have explored the manifold physical scenario 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 observed by Borghini) and the typical polarization time is reduced on moving towards the boundaries of said line. More reasonable behaviours are obtained by reducing the level of microwave saturation or the contact between electrons and nuclei in 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. If 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 the different scenario is discussed in the light of the experimental data currently available in literature, to point out which aspects are suitably accounted and which are not by the declinations of thermal mixing DNP considered here.