Competitive Role of CH4-CH4 and CH-π Interactions in C6H6-(CH4)n Aggregates: The Transition from Dimer to Cluster Features

The intermolecular methane-methane and benzene (Bz)-methane interactions formulated in this paper are suitable to investigate systems of increasing complexity. The proposed CH4-CH4 and Bz-CH4 potential energy functions are indeed applied to study some macroscopic properties of methane and important features of both small Bz-(CH4)(n) (n > 1-10) clusters and Bz surrounded by several CH4 molecules. Relevant parameters of the interaction, derived from molecular polarizability components, have been proved to be useful to describe in a consistent way both size repulsion and dispersion attraction forces. The proposed potential model also allows one to isolate the role of the different intermolecular energy contributions. The spatial distribution of the CH4 molecules in the clusters is investigated by means of molecular dynamics simulations under various conditions, even when methane phase transition from liquid to gas is likely to occur. In addition, several properties, such as radial distribution functions, density values, and mean diffusion coefficients, are analyzed in detail.