First-principles calculation of 11B solid-state NMR parameters of boron-rich compounds II: the orthorhombic phases MgB7 and MgB12C2 and the boron modification γ-B28

• Published in: Physical chemistry chemical physics : PCCP 2021-02, Vol.23 (6), p.3883-3897
• Main Authors: Ludwig, Martin, Hillebrecht, Harald
• Format: Article
• Language: English
• Subjects: Borides; Boron; Boron compounds; Coupling (molecular); Critical point; Density functional theory; Electric fields; Electron density; First principles; Icosahedrons; NMR; Nuclear magnetic resonance; Orthorhombic phase; Parameters; Spectra
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d0cp06073a

Based on the work on referencing 11B nuclear magnetic resonance (NMR) spectra for molecular icosahedral boranes and the subsequent transfer to the rhombohedral boron-rich borides of the α-rB12 type, we show that the magic angle spinning (MAS) NMR spectra of boron-rich borides with four or five symmetry-independent boron atoms can also be calculated. The calculations are performed on the level of density functional theory (DFT) using the gauge-including projector-augmented wave (GIPAW) approach. As model compounds o-MgB12C2 and MgB7 are used, for which the experimental spectra could be calculated in excellent agreement with a deviation of 1 to 2 ppm. Based on the calculations, the different B atoms can be assigned to the respective signals, taking into account the quadrupolar coupling constants Cq from computation of the electric field gradient (EFG) with its main axis Vzz. It is shown that due to the specific geometric conditions of icosahedra, the magnitudes of Vzz for the boron atoms involved in exohedral B–B bonds to neighbouring icosahedra depend only on the valence electron density of the bond critical point and the distance. This also applies to the bonds to the interstitial B2 unit in MgB7, but not to bonds to the heteroatom of the C2 dumbbell in o-MgB12C2. Both results are in line with our previous observations for the rhombohedral species (α-rB12; B12X2 with X = P, As, O). Finally, the spectrum of γ-B28 was calculated, whose structure also contains B12 icosahedra and interstitial B2 dumbbells. Here, a very similar bonding situation is found for the icosahedron, but the calculations show that the situation for the B2 unit is clearly different. In general, the only parameter that needs to be varied to fit calculated and measured spectra is the linewidth, as this cannot be calculated. For the cases of o-MgB12C2 and MgB7 signal areas are related to corresponding site multiplicities. A prerequisite for the successful application of the chosen method seems to be the presence of a semiconductor with a sufficiently large band gap, which is the case for the compounds investigated.