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DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

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Pigliapochi, R 
Pell, AJ 
Seymour, ID 
Grey, CP 
Ceresoli, D 


Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centers. We demonstrate how the single-ion electron paramagnetic resonance g tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the g tensor with density functional theory to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, 𝛔σs. The method is applied to a series of olivine-type LiTMPO4 materials (with TM=Mn, Fe, Co, and Ni) and the corresponding 7Li and 31P NMR spectra are simulated. We analyze the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the LiTMPO4 series, in which the magnitudes and signs of the nonrelativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.



51 Physical Sciences, 34 Chemical Sciences, 3406 Physical Chemistry

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Physical Review B

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American Physical Society
European Commission (317127)
RP acknowledges financial support from the People Programme (Marie Curie Ac- tions) of the European Union’s Seventh Framework Pro- gramme (FP7/2007-2013) under REA grant agreement n◦ 317127. Via our membership of the U.K.’s HPC Materials Chemistry Consortium, which is funded by EPSRC (n ◦ EP/L000202), this work made use of the facilities of ARCHER, the U.K.’s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC’s High End Computing Programme. Research was also carried out at the Center for Functional Nanomaterials, Brookhaven National Lab- oratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract n◦ DE-AC02-98CH10886.