NMR Crystallography: Evaluation of Hydrogen Positions in Hydromagnesite by 13C{1H} REDOR Solid‐State NMR and Density Functional Theory Calculation of Chemical Shielding Tensors

Abstract

Solid-state NMR measurements coupled with density functional theory (DFT) calculations demonstrate how hydrogen positions can be refined in a crystalline system. The precision afforded by rotational-echo double-resonance (REDOR) NMR to interrogate 13 C-1 H distances is exploited along with DFT determinations of the 13 C tensor of carbonates (CO3 2- ). Nearby 1 H nuclei perturb the axial symmetry of the carbonate sites in the hydrated carbonate mineral, hydromagnesite [4 MgCO3 ⋅Mg(OH)2 ⋅4 H2 O]. A match between the calculated structure and solid-state NMR was found by testing multiple semi-local and dispersion-corrected DFT functionals and applying them to optimize atom positions, starting from X-ray diffraction (XRD)-determined atomic coordinates. This was validated by comparing calculated to experimental 13 C{1 H} REDOR and 13 C chemical shift anisotropy (CSA) tensor values. The results show that the combination of solid-state NMR, XRD, and DFT can improve structure refinement for hydrated materials.