Dimers of polycyclic aromatic hydrocarbons: the missing pieces in the soot formation process.

The soot nucleation process, defined as the transition from molecular precursors to condensed matter, is the less understood step in the whole soot formation process. The possibility that polycyclic aromatic hydrocarbon (PAH) dimers, especially those containing moderate-sized PAHs, can play a major role in soot nucleation is a very controversial issue. Although PAH dimers have often been considered as potential soot precursors, their formation is not thermodynamically favored at a typical flame temperature, their binding energies being considered too weak to allow them to survive in this environment. Hereby, we report experimental evidence supporting the existence of PAH dimers in the proximity of the soot nucleation region of a methane laminar diffusion flame that gives strong evidence for the nucleation process to be kinetically rather than thermodynamically controlled.