The EFG Rosetta Stone: translating between DFT calculations and solid state NMR experiments

Abstract

We present a comprehensive study on the best practices for integrating first principles simulations in experimental quadrupolar solid-state nuclear magnetic resonance (SS-NMR), exploiting the synergies between theory and experiment for achieving the optimal interpretation of both. Most high performance materials (HPMs), such as battery electrodes, exhibit complex SS-NMR spectra due to dynamic effects or amorphous phases. NMR crystallography for such challenging materials requires reliable, accurate, efficient computational methods for calculating NMR observables from first principles for the transfer between theoretical material structure models and the interpretation of their experimental SS-NMR spectra. NMR-active nuclei within HPMs are routinely probed by their chemical shielding anisotropy (CSA). However, several nuclear isotopes of interest, e.g. ⁷Li and ²⁷Al, have a nuclear quadrupole and experience additional interactions with the surrounding electric field gradient (EFG). The quadrupolar interaction is a valuable source of information about atomistic structure, and in particular, local symmetry, complementing the CSA. As such, there is a range of different methods and codes to choose from for calculating EFGs, from all-electron to plane wave methods. We benchmark the accuracy of different simulation strategies for computing the EFG tensor of quadrupolar nuclei with plane wave density functional theory (DFT) and study the impact of the material structure as well as the details of the simulation strategy. Especially for small nuclei with few electrons, such as ⁷Li, we show that the choice of physical approximations and simulation parameters has a large effect on the transferability of the simulation results. To the best of our knowledge, we present the first comprehensive reference scale and literature survey for ⁷Li quadrupolar couplings. The results allow us to establish practical guidelines for developing the best simulation strategy for correlating DFT to experimental data extracting the maximum benefit and information from both, thereby advancing further research into HPMs.