Finite, heterogeneous Van der Waals complexes consisting of an aromatic molecule and rare gas atoms have been the subject of numerous studies, both theoretical [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11] and experimental. [1, 3, 5, 12] However, difficulties arise in comparison between these studies due to uncertainties in the mechanism of formation, energy distribution and stability of the clusters [4, 5]. In this work we model the intermolecular interactions of BzAr clusters using a combination of atom-atom dispersion-repulsion, distributed multipoles [13, 14] and polarisabilities. We show how the relative importance of terms in the energy varies with the number of Ar atoms and find that the minimum energy and transition state structures are largely unaffected by different sets of model parameters, at least in terms of their geometries. However, the energetic ordering of the minima is sensitive to changes in the potential and we can rationalise this in terms of the specific parameters. In addition, we present a selection of reaction pathways for some of the smaller clusters and compare them with previous suggestions. In our dynamical studies we examine systems at constant temperature (canonical) and at constant energy (microcanonical). Inherent difficulties exist for these simulations due to the complexity of the configuration space. We demonstrate the effect of restricted sampling of configuration space (non-ergodicity) for calculating thermodynamic quantities with Monte Carlo methods and how these can be overcome by using the Jump-Walking proposed by Frantz, Freeman and Doll [15]. We also use the sampled potential energy distribution in a histogram approach [16, 17] to study both the canonical and the microcanonical ensembles. We compare these results with direct microcanonical Molecular Dynamics simulations to estimate structural transition barriers and escape times.