Rotational dynamics and polymerization of C₆₀ in C₆₀-cubane crystals: A molecular dynamics study

We report classical and tight-binding molecular dynamics simulations of the C$_{60}$ fullerene and cubane molecular crystal in order to investigate intermolecular dynamics and polymerization processes. Our results show that, for 200 K and 400 K, cubane molecules remain basically fixed, presenting only thermal vibrations, while C$_{60}$ fullerenes show rotational motions. Fullerenes perform "free" rotational motions at short times ($\lesssim$ 1 ps), small amplitude hindered rotational motions (librations) at intermediate times, and rotational diffusive dynamics at long times ($\gtrsim$ 10 ps). The mechanisms underlying these dynamics are presented. Random copolymerization among cubanes and fullerenes were observed when temperature is increased, leading to the formation of a disordered structure. Changes in the radial distribution function and electronic density of states indicate the coexistence of amorphous and crystalline phases. The different conformational phases that cubanes and fullerenes undergo during the copolymerization process are discussed.