Vibrations and Thermodynamics of Clusters of Polycyclic Aromatic Hydrocarbon Molecules:  The Role of Internal Modes

The vibrational spectra of clusters of coronene molecules are theoretically calculated using a mixed quantum/classical scheme, each molecule being described by a tight-binding Hamiltonian, the intermolecular forces being provided by explicit Lennard-Jones and point charge sites. The normal modes of vibrations are shown to exhibit significant variations upon clustering. In particular, for large clusters intra- and intermolecular modes tend to mix and fill the mid-infrared range. We also calculate the heat capacity of the (C₂₄H₁₂)₈ cluster as a function of temperature, emphasizing the isomerizations that take place during melting. Quantum delocalization effects, as obtained from the Pitzer−Gwinn semiclassical approximation, are important enough to wash out all signatures of the structural transitions on the caloric curve. On the basis of a simple two-state model we estimate that clusters containing about 300 molecules are required for melting to be detected on the caloric curve.