Carroll, Anne M., Sandra Eaton, Gareth Eaton, and Kurt W. Zilm. “Electron Spin Relaxation of P1 Centers in Synthetic Diamonds with Potential as B1 Standards for DNP Enhanced NMR.” Journal of Magnetic Resonance 322 (January 2021): 106875.
https://doi.org/10.1016/j.jmr.2020.106875.
The microwave magnetic field, B1 , in the non-resonant structures typically used for DNPenhanced NMR is relatively small, so calibration via continuous wave (CW) power saturation requires a sample with longer spin lattice relaxation times than the samples used as CW standards in X-band cavities. HPHT diamonds have strong, easily observed EPR signals from P1 centers (nitrogen defects), and are indefinitely stable. This makes HPHT diamonds attractive as secondary standards for calibration of electron B1 field strength in a variety of experimental arrangements. The concentrations of P1 centers is also typically in the 30-200 ppm range, or equivalently 10-60 mM, and therefore the EPR relaxation observed is relevant to DNP enhanced NMR employing free radical polarizing agents at similar concentrations. Pulsed and CW saturation relaxation measurements T1 and T2 are compared at X-band. Under CW conditions the relevant T1T2 product of time constants in our samples at room temperature is found to be dominated by electron-electron spin diffusion, and the product is large enough that saturation will be possible with the B1 of typical DNP systems. The similarity of T1 and T2 values obtained by pulse measurements at X-band and Q-band suggests that the X-band results can be extrapolated to the higher EPR frequencies used for DNP experiments. The electron spin dynamics observed here in HPHT diamond samples identify them as useful model systems to better delineate the interplay of electron spin relaxation, magic angle spinning, and inhomogeneous microwave irradiation as they affect DNP enhancement.