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  • Accepted Manuscript: Predicting anisotropic thermal displacements for hydrogens from solid-state NMR: a study on hydrogen bonding in polymorphs of palmitic acid
Title: Predicting anisotropic thermal displacements for hydrogens from solid-state NMR: a study on hydrogen bonding in polymorphs of palmitic acid
The hydrogen-bonding environments at the COOH moiety in eight polycrystalline polymorphs of palmitic acid are explored using solid-state NMR. Although most phases have no previously reported crystal structure, measured 13 C chemical shift tensors for COOH moieties, combined with DFT modeling establish that all phases crystallize with a cyclic dimer ( R 22(8)) hydrogen bonding arrangement. Phases A 2 , B m and E m have localized OH hydrogens while phase C has a dynamically disordered OH hydrogen. The phase designated A s is a mix of five forms, including 27.4% of B m and four novel phases not fully characterized here due to insufficient sample mass. For phases A 2 , B m , E m , and C the anisotropic uncertainties in the COOH hydrogen atom positions are established using a Monte Carlo sampling scheme. Sampled points are retained or rejected at the ±1 σ level based upon agreement of DFT computed 13 COOH tensors with experimental values. The collection of retained hydrogen positions bear a remarkable resemblance to the anisotropic displacement parameters ( i.e. thermal ellipsoids) from diffraction studies. We posit that this similarity is no mere coincidence and that the two are fundamentally related. The volumes more » of NMR-derived anisotropic displacement ellipsoids for phases with localized OH hydrogens are 4.1 times smaller than those derived from single crystal X-ray diffraction and 1.8 times smaller than the volume of benchmark single crystal neutron diffraction values. « less
Authors:
; ; ;
Award ID(s):
1710671
Publication Date:
NSF-PAR ID:
10067384
Journal Name:
Physical Chemistry Chemical Physics
Volume:
20
Issue:
13
Page Range or eLocation-ID:
8475 to 8487
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
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