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Efficient prediction of Nucleus Independent Chemical Shifts for polycyclic aromatic hydrocarbons

Accepted version
Peer-reviewed

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Article

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Authors

Kilymis, Dimitrios 
Bartok, Albert 
Pickard, Christopher  ORCID logo  https://orcid.org/0000-0002-9684-5432
Merlet, Celine 

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 magnitudes faster than DFT calculations, is very promising and can be further refined in order to study more complex systems.

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Journal Title

Physical Chemistry Chemical Physics

Conference Name

Journal ISSN

1463-9076

Volume Title

Publisher

RSC

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All rights reserved
Sponsorship
Royal Society (WM150023)
Engineering and Physical Sciences Research Council (EP/P022596/1)