A DFT study of the interaction between large PAHs and atomic chlorine or hydrogen chloride molecule: Toward a modelling of the influence of chlorinated species on the trapping of water by soot

First-principle calculations have been performed to characterize the interaction of chlorinated species (HCl and Cl) with large polycyclic aromatic hydrocarbon (PAH) molecules and radicals. Whereas the characterization of the interaction process on the face of the PAH molecules requires taking into account long-range dispersion interactions in the calculations, trapping at the edge of PAH radicals involves stronger interactions that lead to the dissociation of the HCl molecule. Then, the first steps of water adsorption on the corresponding chlorinated species has been characterized, showing that chlorine may act as an efficient nucleation center for water molecules on such aromatic systems mimicking part of the carbonaceous surfaces that are likely present in soot. These results represent a first but necessary step for a better understanding of soot behavior in industrial or domestic fire situations.

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