Atomistic insights into the dynamics of binary collisions between gaseous molecules and polycyclic aromatic hydrocarbon dimers

Abstract

Polycyclic aromatic hydrocarbon (PAH) dimers are important intermediates in combustion and soot formation. The scattering dynamics of gaseous molecules colliding with PAH dimers and the subsequent PAH dimer stability are investigated by performing molecular dynamics (MD) simulations. Effects of properties of the surrounding gaseous molecules and PAH dimers as well as temperature are investigated in this study. Depending on the residence time of N₂ molecules trapped by the PAH dimers, two scattering types, that is, specular scattering and inelastic scattering, have been observed, which is correlated to the temperature and the type of the PAH dimer. Specifically, specular scattering preferentially takes place at high temperatures on small PAH dimers, while inelastic scattering tends to happen at low temperatures on large PAH dimers. During collision, energy transfer between the gaseous molecule and the PAH dimer changes the thermodynamic stability of the PAH dimer. Statistical analysis indicates that the decomposition rate of a PAH dimer to PAH monomers is sensitive to temperature and the PAH dimer type. Furthermore, effects of the gaseous molecule type on the PAH dimer stability are considered. The molecular mass of the colliding gaseous molecule is a key factor in determining the PAH dimer stability, as heavier gaseous molecules are more effective in promoting the PAH dimer decomposition. Results from this study indicate that collisions with gaseous molecules decrease the PAH dimer stability, while increasing the PAH dimer size and decreasing the collision temperature both decrease the decomposition rate of the PAH dimer.