Tan, Kong Ooi, Ralph T. Weber, Thach V. Can, and Robert G. Griffin. “Adiabatic Solid Effect.” The Journal of Physical Chemistry Letters, April 20, 2020, 3416–21.
The solid effect (SE) is a two spin dynamic nuclear polarization (DNP) mechanism that enhances the sensitivity in NMR experiments by irradiation of the electron-nuclear spin transitions with continuous wave (CW) microwaves at 𝜔0S ± 𝜔0I, where 𝜔0S and 𝜔0I are electron and nuclear Larmor frequencies, respectively. Using trityl (OX063), dispersed in a 60/40 glycerol/water mixture at 80 K, as a polarizing agent, we show here that application of a chirped microwave pulse, with a bandwidth comparable to the EPR linewidth applied at the SE matching condition, improves the enhancement by a factor of 2.4 over the CW method. Furthermore, the chirped pulse yields an enhancement that is ~20 % larger than obtained with the ramped-amplitude NOVEL (RA-NOVEL), which to date has achieved the largest enhancements in time domain DNP experiments. Numerical simulations suggest that the spins follow an adiabatic trajectory during the polarization transfer; hence, we denote this sequence as an adiabatic solid effect (ASE). We foresee that ASE will be a practical pulsed DNP experiment to be implemented at higher static magnetic fields due to moderate power requirement. In particular, the ASE uses only 13 % of the maximum microwave power required for RA-NOVEL.