Cross-Effect Dynamic Nuclear Polarization Explained: Polarization, Depolarization, and Oversaturation

J Phys Chem Lett. 2019 Feb 7;10(3):548-558. doi: 10.1021/acs.jpclett.8b02834. Epub 2019 Jan 23.

Abstract

The scope of this Perspective is to analytically describe NMR hyperpolarization by the three-spin cross effect (CE) dynamic nuclear polarization (DNP) using an effective Hamiltonian concept. We apply, for the first time, the bimodal operator-based Floquet theory in the Zeeman-interaction frame for two and three coupled spins to derive the known interaction Hamiltonian for CE-DNP. With a unified understanding of CE-DNP, and supported by empirical observation of the state of electron spin polarization under the given experimental conditions, we explain diverse manifestations of CE from oversaturation, enhanced hyperpolarization by broad-band saturation, to nuclear spin depolarization under magic-angle spinning.