Nielsen, Anders Bodholt, José Pedro Albuquerque De Carvalho, David Leslie Goodwin, Nino Wili, and Niels Chr. Nielsen. “Dynamic Nuclear Polarization Pulse Sequence Engineering Using Single-Spin Vector Effective Hamiltonians,” August 16, 2024.
https://doi.org/10.26434/chemrxiv-2024-xkfd6.
Dynamic nuclear polarization (DNP) has proven to be a powerful technique to enhance nuclear spin polarization by transferring the much higher electron spin polarization to the nuclear spins prior to detection. While major attention has been devoted to high-field applications with continuous microwave irradiation, the introduction of fast arbitrary waveform generators is gradually increasing the opportunities to a realization of pulsed DNP. Here, we describe how static-powder DNP pulse sequences may systematically be designed using single-spin vector effective Hamiltonian theory. Particular attention is devoted to the intricate interplay between two important parts of the effective first-order Hamiltonian, namely, the linear field (single-spin) terms, and the Fourier coefficients determining scaling of the bilinear coupling terms mediating polarization transfer. We address two cases. The first operates in the regime where the microwave field amplitude is lower than the nuclear Larmor frequency. Here, we illustrate the predictive strength of single-spin vector model by comparing analytical calculations with experimental DNP results at 9.8 GHz/15 MHz on trityl radicals at 80 K. The second case operates in the high-power regime, where we combine the underlying single-spin vector design principles with numerical non-linear optimization to optimize the balance between the linear terms and the bilinear Fourier coefficients in a figure of merit function. We demonstrate, numerically and experimentally, a broadband DNP pulse sequence PLATO (PoLarizAtion Transfer via non-linear Optimization) with a bandwidth of 80 MHz and optimized for microwave field a with maximum (peak) amplitude of 32 MHz.