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research article

Importance of Nuclear Quantum Effects for NMR Crystallography

Engel, Edgar A.
•
Kapil, Venkat  
•
Ceriotti, Michele  
August 19, 2021
The Journal of Physical Chemistry Letters

The resolving power of solid-state nuclear magnetic resonance (NMR) crystallography depends heavily on the accuracy of computational predictions of NMR chemical shieldings of candidate structures, which are usually taken to be local minima in the potential energy. To test the limits of this approximation, we systematically study the importance of finite-temperature and quantum nuclear fluctuations for H-1, C-13, and N-15 shieldings in polymorphs of three paradigmatic molecular crystals: benzene, glycine, and succinic acid. The effect of quantum fluctuations is comparable to the typical errors of shielding predictions for static nuclei with respect to experiments, and their inclusion improves the agreement with measurements, translating to more reliable assignment of the NMR spectra to the correct candidate structure. The use of integrated machine-learning models, trained on first-principles energies and shieldings, renders rigorous sampling of nuclear fluctuations affordable, setting a new standard for the calculations underlying NMR structure determinations.

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Type
research article
DOI
10.1021/acs.jpclett.1c01987
Web of Science ID

WOS:000687716600006

Author(s)
Engel, Edgar A.
Kapil, Venkat  
Ceriotti, Michele  
Date Issued

2021-08-19

Publisher

AMER CHEMICAL SOC

Published in
The Journal of Physical Chemistry Letters
Volume

12

Issue

32

Start page

7701

End page

7707

Subjects

Chemistry, Physical

•

Nanoscience & Nanotechnology

•

Materials Science, Multidisciplinary

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Science & Technology - Other Topics

•

Materials Science

•

Physics

•

spin coupling-constants

•

chemical-shift

•

1st-principles calculation

•

molecular-dynamics

•

hydrogen-bond

•

benzene i

•

parameters

•

shieldings

•

o-17

•

temperature

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
September 11, 2021
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/181236
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