Can small polyaromatics describe their larger counterparts for local reactions? A computational study on the H-abstraction reaction by an H-atom from polyaromatics

Yonder, Ö. and Schmitz, G. and Hättig, C. and Schmid, R. and Debiagi, P. and Hasse, C. and Locaspi, A. and Faravelli, T.

Volume: 124 Pages: 9626-9637
DOI: 10.1021/acs.jpca.0c07133
Published: 2020

Hydrogen abstraction is one of the crucial initial key steps in the combustion of polycyclic aromatic hydrocarbons. For an accurate theoretical prediction of heterogeneous combustion processes, larger systems need to be treated as compared to pure gas phase reactions. We address here the question on how transferable activation and reaction energies computed for small molecular models are to larger polyaromatics. The approximate transferability of energy contributions is a key assumption for multiscale modeling approaches. To identify efficient levels of accuracy, we start with accurate coupled-cluster and density functional theory (DFT) calculations for different sizes of polyaromatics. More approximate methods as the reactive force-field ReaxFF and the extended semi-empirical tight binding (xTB) methods are then benchmarked against these data sets in terms of reaction energies and equilibrium geometries. Furthermore, we analyze the role of bond-breaking and relaxation energies, vibrational contributions, and post-Hartree-Fock correlation corrections on the reaction, and for the activation energies, we analyze the validity of the Bell-Evans-Polanyi and Hammond principles. First, we find good transferability for this process and that the predictivity of small models at high theoretical levels is way superior than any approximate method can deliver. Second, ReaxFF can serve as a qualitative exploration method, whereas GFN2-xTB in combination with GFN1-xTB appears as a favorable tool to bridge between DFT and ReaxFF so that we propose a multimethod scheme with employing ReaxFF, GFN1/ GFN2-xTB, DFT, and coupled cluster to cope effectively with such a complex reactive system. © 2020 American Chemical Society

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