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research article

Theory and simulations of homonuclear three-spin systems in rotating solids

de Almeida, Bruno Simoes  
•
Moutzouri, Pinelopi  
•
Stevanato, Gabriele  
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August 28, 2021
Journal Of Chemical Physics

The homonuclear dipolar coupling is the internal spin interaction that contributes the most to the line shapes in magic-angle-spinning (MAS) H-1 NMR spectra of solids, and linewidths typically extend over several hundred Hertz, limiting the H-1 resolution. Understanding and reducing this contribution could provide rich structural information for organic solids. Here, we use average Hamiltonian theory to study two- and three-spin systems in the fast MAS regime. Specifically, we develop analytical expressions to third order in the case of two and three inequivalent spins (I = 1/2). The results show that the full third-order expression of the Hamiltonian, without secular approximations or truncation to second order, is the description that agrees the best, by far, with full numerical calculations. We determine the effect on the NMR spectrum of the different Hamiltonian terms, which are shown to produce both residual shifts and splittings in the three-spin systems. Both the shifts and splittings have a fairly complex dependence on the spinning rate with the eigenstates having a polynomial.r dependence. The effect on powder line shapes is also shown, and we find that the anisotropic residual shift does not have zero average so that the powder line shape is broadened and shifted from the isotropic position. This suggests that in H-1 MAS spectra, even at the fastest MAS rates attainable today, the positions observed are not exactly the isotropic shifts. (c) 2021 Author(s).

  • Details
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Type
research article
DOI
10.1063/5.0055583
Web of Science ID

WOS:000755394400002

Author(s)
de Almeida, Bruno Simoes  
Moutzouri, Pinelopi  
Stevanato, Gabriele  
Emsley, Lyndon  
Date Issued

2021-08-28

Published in
Journal Of Chemical Physics
Volume

155

Issue

8

Article Number

084201

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

magnetic-resonance spectra

•

state nmr-spectroscopy

•

high-resolution nmr

•

multiple-pulse nmr

•

100 khz mas

•

spin-diffusion

•

h-1-nmr

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LRM  
FunderGrant Number

FNS

200020_178860

Available on Infoscience
February 28, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/185766
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