Coarse-grained modeling of the nucleation of polycyclic aromatic hydrocarbons into soot precursors

Abstract

The aggregation and physical growth of polycyclic aromatic hydrocarbon (PAH) molecules was simulated using a coarse-grained (CG) approach based on the Paramonov–Yaliraki (PY) potential and a stochastic Monte Carlo framework, following earlier efforts in which the structure [Phys. Chem. Chem. Phys., 2016, 18, 13736] and equilibrium thermodynamics [Phys. Chem. Chem. Phys., 2017, 19, 1884] were investigated and critically compared to the predictions of all-atom models. Homomolecular and heteromolecular assemblies of pyrene, coronene, and circumcoronene were considered at various temperatures and compositions, and the distributions of aggregation products were characterized. Under the simulated conditions, and in agreement with earlier studies, the clusters are rather small and, in the case of pyrene-rich systems, only formed below 1000 K. The clusters obtained by spontaneous aggregation of isolated molecules are statistically analysed. For the selected sizes of tetramers and octamers, broad distributions of isomers are obtained with a clear entropic stabilization. In heteronuclear assemblies, our results suggest a minor spontaneous segregation towards pure and equi concentrations at variance with purely statistical expectations.