Theoretical gas to liquid shift of 15 N isotropic nuclear magnetic shielding in nitromethane using ab initio molecular dynamics and GIAO/GIPAW calculations

Chemical shift requires the knowledge of both the sample and a reference magnetic shielding. In few cases as nitrogen (15N), the standard experimental reference corresponds to its liquid phase. Theoretical estimate of NMR magnetic shielding parameters of compounds in their liquid phase is then manda...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2015, Vol.17 (18), p.12222-12227
Main Authors: Gerber, Iann C., Jolibois, Franck
Format: Article
Language:English
Subjects:
Chemical Sciences
or physical chemistry
Theoretical and
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Summary:Chemical shift requires the knowledge of both the sample and a reference magnetic shielding. In few cases as nitrogen (15N), the standard experimental reference corresponds to its liquid phase. Theoretical estimate of NMR magnetic shielding parameters of compounds in their liquid phase is then mandatory but usually replaced by an easily-get gas phase value, forbidding direct comparisons with experiments. We propose here to combine ab initio molecular dynamic simulations with the calculations of magnetic shielding using GIAO approach on extracted cluster's structures from MD. Using several computational strategies, we manage to accurately calculate 15N magnetic shielding of nitromethane in its liquid phase. Theoretical comparison between liquid and gas phase allows us to extrapolate an experimental value for the 15N magnetic shielding of nitromethane in gas phase between −121.8 and −120.8 ppm.
ISSN:1463-9076
1463-9084
DOI:10.1039/C5CP00722D