Simulation of nitrogen nuclear spin magnetization of liquid solved nitroxides

Abstract

Nitroxide radicals are widely used in electron paramagnetic resonance (EPR) applications. Nitroxides are stable organic radicals containing the N–O˙ group with hyperfine coupled unpaired electron and nitrogen nuclear spins. In the past, much attention was devoted to studying nitroxide EPR spectra and electron spin magnetization evolution under various experimental conditions. However, the dynamics of nitrogen nuclear spin has not been investigated in detail so far. In this work, we performed quantitative prediction and simulation of nitrogen nuclear spin magnetization evolution in several magnetic resonance experiments. Our research was focused on fast rotating nitroxide radicals in liquid solutions. We used a general approach allowing us to compute electron and nitrogen nuclear spin magnetization from the same time-dependent spin density matrix obtained by solving the Liouville/von Neumann equation. We investigated the nitrogen nuclear spin dynamics subjected to various radiofrequency magnetic fields. Furthermore, we predicted a large dynamic nuclear polarization of nitrogen upon nitroxide irradiation with microwaves and analyzed its effect on the nitroxide EPR saturation factor.