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Efficient prediction of nucleus independent chemical shifts for polycyclic aromatic hydrocarbons

Kilymis, Dimitrios and Bartók, Albert P. and Pickard, Chris J. and Forse, Alexander C. and Merlet, Céline Efficient prediction of nucleus independent chemical shifts for polycyclic aromatic hydrocarbons. (2020) Physical Chemistry Chemical Physics, 22 (24). 13746-13755. ISSN 1463-9076

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Official URL: https://doi.org/10.1039/D0CP01705A

Abstract

Nuclear Magnetic Resonance (NMR) is one of the most powerful experimental techniques to characterize the structure of molecules and confined liquids. Nevertheless, the complexity of the systems under investigation usually requires complementary computational studies to interpret the NMR results. In this work we focus on polycyclic aromatic hydrocarbons (PAHs), an important class of organic molecules which have been commonly used as simple analogues for the spectroscopic properties of more complex systems, such as porous disordered carbons. We use Density Functional Theory (DFT) to calculate 13C chemical shifts and Nucleus Independent Chemical Shifts (NICS) for 34 PAHs. The results show a clear molecular size dependence of the two quantities, as well as the convergence of the 13C NMR shifts towards the values observed for graphene. We then present two computationally cheap models for the prediction of NICS in simple PAHs. We show that while a simple dipolar model fails to produce accurate values, a perturbative tight-binding approach can be successfully applied for the prediction of NICS in this series of molecules, including some non-planar ones containing 5- and 7-membered rings. This model, one to two orders of magnitude faster than DFT calculations, is very promising and can be further refined in order to study more complex systems.

Item Type:Article
Audience (journal):International peer-reviewed journal
Uncontrolled Keywords:
Institution:French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE)
Other partners > Collège de France (FRANCE)
Other partners > Ecole Nationale Supérieure de Chimie de Paris - ENSCP (FRANCE)
Other partners > Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE)
Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Other partners > Institut polytechnique de Grenoble (FRANCE)
Other partners > Sorbonne Université (FRANCE)
Other partners > University of Cambridge (UNITED KINGDOM)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Université de Nantes (FRANCE)
Other partners > Université de Picardie Jules Verne (FRANCE)
Other partners > University of Warwick (UNITED KINGDOM)
Other partners > Science and Technology Facilities Council - STFC (UNITED KINGDOM)
Other partners > Tohoku University (JAPAN)
Other partners > University of California - UC Berkeley (USA)
Other partners > Université de Pau et des Pays de l'Adour - UPPA (FRANCE)
Other partners > Université de Grenoble (FRANCE)
Other partners > Université de Haute Alsace - UHA (FRANCE)
Other partners > Université de Montpellier (FRANCE)
Laboratory name:
Funders:
European Research Council (ERC) - HPC resources of CALMIP supercomputing center
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Deposited On:24 Jul 2020 10:21

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