Frequency-Swept Integrated and Stretched Solid Effect Dynamic Nuclear Polarization.

We investigate a new time domain approach to dynamic nuclear polarization (DNP), the frequency-swept integrated solid effect (FS-ISE), utilizing a high power, broadband 94 GHz (3.35 T) pulse EPR spectrometer. The bandwidth of the spectrometer enabled measurement of the DNP Zeeman frequency/field profile that revealed two dominant polarization mechanisms, the expected ISE, and a recently observed mechanism, the stretched solid effect (S2E). At 94 GHz, despite the limitations in the microwave chirp pulse length (10 µs) and the repetition rate (2 kHz), we obtained signal enhancements up to ∼70 for the S2E and ∼50 for the ISE. The results successfully demonstrate the viability of the FS-ISE and S2E DNP at a frequency 10 times higher than previous studies. Our results also suggest that these approaches are candidates for implementation at higher magnetic fields.