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Calculation of NMR chemical shifts in carbohydrates with ONIOM: A study of the conformers of beta-D-glucopyranose

Rickard, G.A., Karadakov, P.B., Webb, G.A. and Morokuma, K. (2003) Calculation of NMR chemical shifts in carbohydrates with ONIOM: A study of the conformers of beta-D-glucopyranose. Journal of Physical Chemistry A, 107 (2). pp. 292-300. ISSN 1089-5639

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Abstract

The two-layer ONIOM2(MP2-GIAO:HF-GIAO) (our own n-layer integrated molecular orbital and molecular mechanics approach, in which a small model system containing the nuclei of interest is described at the MP2-GIAO level of theory, and the rest of the moleculeusing the HF-GIAO method) ansatz is applied to the calculation of 13C, 1H, and 17O NMR chemical shifts in the 4C1 G+, 4C1 G-, 4C1 T, 1C4 G+, and 1C4 G- conformers of β-d-glucopyranose. It is shown that with an appropriate choice of the model system this construction yields chemical shifts that represent close approximations to the corresponding MP2-GIAO values for the entire molecule, which makes it suitable for post-HF NMR chemical shift calculations on higher carbohydrates. The best correlations between experimental and theoretical 13C chemical shifts are achieved using the results of the calculations on the 4C1 G+ and 4C1 G- conformers, which is in agreement with the experimental evidence about the predominance of these two forms in aqueous solution.

Item Type: Article
Institution: The University of York
Academic Units: The University of York > Chemistry (York)
Depositing User: York RAE Import
Date Deposited: 20 Apr 2009 11:56
Last Modified: 20 Apr 2009 11:56
Published Version: http://dx.doi.org/10.1021/jp027279l
Status: Published
Publisher: American Chemical Society
Identification Number: 10.1021/jp027279l
URI: http://eprints.whiterose.ac.uk/id/eprint/6844

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