Perras, Frédéric A., Muralikrishna Raju, Scott L. Carnahan, Dooman Akbarian, Adri C. T. van Duin, Aaron J. Rossini, and Marek Pruski. “Full-Scale Ab Initio Simulation of Magic-Angle-Spinning Dynamic Nuclear Polarization.” The Journal of Physical Chemistry Letters 11, no. 14 (July 16, 2020): 5655–60.
https://doi.org/10.1021/acs.jpclett.0c00955.
Theoretical models aimed at describing magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) NMR have great potential in facilitating the in silico design of DNP polarizing agents and formulations but must typically face a trade-off between the accuracy of a strict quantum mechanical description, and the need for using realistically large spin systems, for instance using phenomenological models. Here, we show that the use of aggressive state-space restrictions and an optimization strategy allows full-scale ab initio MAS-DNP simulations of spin systems containing thousands of nuclei. Our simulations are shown to reproduce experimental DNP enhancements quantitatively, including their MAS rate dependence, for both frozen solutions and solid materials. They also reveal the importance of a previously unrecognized structural feature found in some polarizing agents that helps minimize the sensitivity losses imposed by the spin diffusion barrier.