Microwave-free dynamic nuclear polarization via sudden thermal jumps

TL;DR

This paper proposes a microwave-free method for dynamic nuclear polarization that uses thermal jumps and RF pulses to polarize nuclear spins efficiently, especially at high magnetic fields, avoiding the need for microwave manipulation.

Contribution

It introduces a novel cyclic protocol combining thermal jumps and RF pulses to achieve nuclear polarization without microwaves, leveraging level anti-crossings and spin relaxation differences.

Findings

Efficient nuclear polarization achieved without microwave excitation.

The method is effective at high magnetic fields.

Transient electronic spin bath out of equilibrium enhances polarization.

Abstract

Dynamic Nuclear Polarization (DNP) presently stands as the preferred strategy to enhance the sensitivity of nuclear magnetic resonance measurements, but its application relies on the use of high-frequency microwave to manipulate electron spins, an increasingly demanding task as the applied magnetic field grows. Here we investigate the dynamics of a system hosting a polarizing agent formed by two distinct paramagnetic centers near a level anti-crossing. We theoretically show that nuclear spins polarize efficiently under a cyclic protocol that combines alternating thermal jumps and radio-frequency pulses connecting hybrid states with opposite nuclear and electronic spin alignment. Central to this process is the difference between the spin-lattice relaxation times of either electron spin species, transiently driving the electronic spin bath out of equilibrium after each thermal jump. Without the need for microwave excitation, this route to enhanced nuclear polarization may prove convenient, particularly if the polarizing agent is designed to feature electronic level anti-crossings at high magnetic fields.