RESUMEN
Solid-state nuclear magnetic resonance (ssNMR) has received extensive attention in characterizing alkali-ion battery materials because it is highly sensitive for probing the local environment and dynamic information of atoms/ions. However, precise spectral assignment cannot be carried out by conventional DFT for high-rate battery materials at room temperature. Herein, combining DFT calculation of paramagnetic shift and deep potential molecular dynamics (DPMD) simulation to achieve the converged Na+ distribution at hundreds of nanoseconds, we obtain the statistically averaged paramagnetic shift, which is in excellent agreement with ssNMR measurements. Two 23 Na shifts induced by different stacking sequences of transition metal layers are revealed in the fast chemically exchanged NMR spectra of P2-type Na2/3 (Mg1/3 Mn2/3 )O2 for the first time. This DPMD simulation auxiliary protocol can be beneficial to a wide range of ssNMR analysis in fast chemically exchanged material systems.
RESUMEN
The lithium NMR shifts of three paramagnetic materials important in the charging/discharging processes of lithium vanadium phosphate cathode materials have been studied by large-scale quantum-chemical methodology. Namely, the 7Li NMR shifts of the fully lithiated Li3V2(PO4)3 (LVP3.0), and of the partly delithiated Li2.5V2(PO4)3 (LVP2.5) and Li2V2(PO4)3 (LVP2.0), have been computed and analyzed using a recently proposed approach (A. Mondal, M. Kaupp J. Phys. Chem. C 123 (2019) 8387-8405) that accounts for the Fermi-contact, pseudo-contact, as well as orbital shifts, combining periodic computations with an incremental cluster model. LVP3.0 and LVP2.0 exhibit three and two unique Li sites, respectively, which could be assigned to their experimental 7Li NMR signals. In case of LVP2.0, the computations clearly assigned the signals at 143â¯ppm and 77â¯ppm to the Li(1) and Li(2) sites, respectively, even though the latter is connected to Vb(+III d2 sites and the former to Va(+IV) d1 sites. LVP2.5 is the most complex of these three materials, exhibiting a 50% occupation of Li(3) sites, which generates much more complicated Li NMR spectra with seven peaks that partly are closely spaced. Exploring three different occupation patterns, the computations can clearly assign five of the seven signals to one type of Li site and give most probable assignments for the two remaining signals. Notably, the calculations support seven signals to be assigned to LVP2.5, while previous interpretations took two of the signals as being entirely due to contamination by LVP2.0. The accuracy of the computations could probably be improved further by full DFT optimization of large super-cell structures. This work suggests that first-principles computations of NMR shifts of extended paramagnetic solids provide an important tool for the analysis of even rather complex NMR spectra.
RESUMEN
By N,N addition of NO to the norbonane annulated borane-phosphane Frustrated Lewis pair (FLP) 1 a five-membered heterocyclic persistent aminoxyl radical 2 and its diamagnetic hydroxylamine reduction product 3 are prepared, and the comprehensive multinuclear solid state NMR characterization ((1)H, (11)B, (19)F, (31)P) of these FLP adducts is reported. Signal quantification experiments using a standard addition method reveal that the (11)B and (31)P NMR signals observed in 2 actually arise from molecular impurities of 3 embedded in the paramagnetic crystal. In contrast analogous quantification experiments reveal that the (1)H and (19)F MAS-NMR spectra originate from spin-carrying molecules. Peak assignments are based on DFT-calculated Mulliken spin densities, which lead to the surprising result that the largest paramagnetic shift affecting a proton NMR resonance in 2 originates from intermolecular interactions. For the (19)F nuclei, experiments and calculations indicate that paramagnetic shift effects are very small. In this case, assignments are based on DFT chemical shift calculations carried out on diamagnetic 3 and (19)F((11)B) Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) experiments. The set of experiments described here defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.