Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

Dračínský, Martin; Hodgkinson, Paul

doi:10.1002/chem.201303496

Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

Dračínský, Martin; Hodgkinson, Paul

Authors

Martin Dračínský

Professor Paul Hodgkinson paul.hodgkinson@durham.ac.uk
Professor

Abstract

The influence of nuclear delocalisation on NMR chemical shifts in molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory calculations of shielding tensors. Nuclear quantum effects are shown to explain previously observed systematic deviations in correlations between calculated and experimental chemical shifts, with particularly large PIMD-induced changes (up to 23 ppm) observed for carbon atoms in methyl groups. The PIMD approach also enables isotope substitution effects on chemical shifts and J couplings to be predicted in excellent agreement with experiment for both isolated molecules and molecular crystals. An approach based on convoluting calculated shielding or coupling surfaces with probability distributions of selected bond distances and valence angles obtained from PIMD simulations is used to calculate isotope effects.

Citation

Dračínský, M., & Hodgkinson, P. (2014). Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics. Chemistry - A European Journal, 20(8), 2201-2207. https://doi.org/10.1002/chem.201303496

Journal Article Type	Article
Online Publication Date	Jan 16, 2014
Publication Date	Feb 17, 2014
Deposit Date	Jun 10, 2014
Publicly Available Date	Jan 16, 2015
Journal	Chemistry - A European Journal
Print ISSN	0947-6539
Electronic ISSN	1521-3765
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	20
Issue	8
Pages	2201-2207
DOI	https://doi.org/10.1002/chem.201303496
Keywords	Density functional calculations, Isotope effects, NMR spectroscopy, Nuclear delocalisation, Path integral molecular dynamics.

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Copyright Statement
This is the peer reviewed version of the following article: Dračínský, M. and Hodgkinson, P. (2014), Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics. Chemistry - A European Journal, 20 (8): 2201-2207, which has been published in final form at http://dx.doi.org/10.1002/chem.201303496. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for self-archiving.