Recent trends in the investigation of dynamical processes occurring in binary van der Waals clusters are reviewed. We demonstrate the complexity of the underlying cluster dynamics even for very elementary rare gas systems where the interaction between the individual cluster constituents can be well described by simple, pairwise additive, spherical Lennard-Jones potentials. Using molecular dynamics simulations, we have explored the fundamental mechanisms occurring during and after the “pick-up” of Ne, SiF₄, Kr, and Xe dopants by Ar_n clusters with n ranging from 53 to 5000 atoms for “quasi- experimental” conditions.  Both Ne and SiF₄ are shown to normally reside in cluster surface states. Matrix states are the most probable location for Kr and Xe atoms. The penetration depth depends crucially on cluster size, cluster velocity, nature of the dopant, buffer gas pressure, and length of the pick-up region. Due to their very different interatomic distances and potential well depths, Kr pick-up normally leads to nearly perfectly structured fcc mixed clusters with the dopants in substitution positions while Xe pick-up results in clusters with large amorphous, glass-like domains. Consequently, we find diffusion coefficients in the Ar clusters that are larger for Xe than for Kr dopants at a given temperature in spite of the higher mass of Xe. As a result, we observe for Xe a significant tendency to segregation leading to the formation of a highly inhomogeneous cluster surface. For high enough doping rates, we find a strong solvation effect for both Xe and SiF₄ impurities. Finally, we show that the results of our simulations are very well suited to interpret our recent experimental results concerning the surface scattering of binary vander Waals clusters.