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Towards accurate predictions of proton NMR parameters in molecular solids

Dracinsky, Martin; Vícha, Jan; Bártová, Kateřina; Hodgkinson, Paul

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Authors

Martin Dracinsky

Jan Vícha

Kateřina Bártová



Abstract

The factors contributing to the accuracy of quantum‐chemical calculations of proton NMR chemical shifts in molecular solids are systematically investigated. Proton chemical shifts of six solid amino acids with hydrogen atoms in various bonding environments (CH, CH 2 , CH 3 , OH, SH and NH 3 ) were determined experimentally using ultra‐fast magic‐angle spinning and proton‐detected 2D NMR experiments. The standard DFT method commonly used for the calculations of NMR parameters of solids is shown to provide chemical shifts that deviate from experiment by up to 1.5 ppm. The effects of the computational level (hybrid DFT functional, coupled‐cluster calculation, inclusion of relativistic spin‐orbit coupling) are thoroughly discussed. The effect of molecular dynamics and nuclear quantum effects are investigated using path‐integral molecular dynamics (PIMD) simulations. It is demonstrated that the accuracy of the calculated proton chemical shifts is significantly better when these effects are included in the calculations.

Citation

Dracinsky, M., Vícha, J., Bártová, K., & Hodgkinson, P. (2020). Towards accurate predictions of proton NMR parameters in molecular solids. ChemPhysChem, 21(18), 2075-2083. https://doi.org/10.1002/cphc.202000629

Journal Article Type Article
Acceptance Date Jul 20, 2020
Online Publication Date Aug 26, 2020
Publication Date 2020
Deposit Date Jul 21, 2020
Publicly Available Date Mar 29, 2024
Journal ChemPhysChem
Print ISSN 1439-4235
Electronic ISSN 1439-7641
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 21
Issue 18
Pages 2075-2083
DOI https://doi.org/10.1002/cphc.202000629

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Copyright Statement
This is the peer reviewed version of the following article: Dracinsky, Martin, Vícha, Jan, Bártová, Kateřina & Hodgkinson, Paul (2020). Towards accurate predictions of proton NMR parameters in molecular solids. ChemPhysChem 21(18): 2075-2083 which has been published in final form at https://doi.org/10.1002/cphc.202000629. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.





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