Chemical dynamics simulations were used to study Bz + Na+(Bz) → Na+(Bz)2∗ association and the ensuing dissociation of the Na+(Bz)2∗ cluster (Bz = benzene). An interesting and unexpected reaction found from the simulations is direct displacement, for which the colliding Bz molecule displaces the Bz molecule attached to Na+, forming Na+(Bz). The rate constant for Bz + Na+(Bz) association was calculated at 750 and 1000 K, and found to decrease with increase in temperature. By contrast, the direct displacement rate constant increases with temperature. The cross section and rate constant for direct displacement are approximately an order of magnitude lower than those for association. The Na+(Bz)2∗ cluster, formed by association, dissociates with a biexponential probability, with the rate constant for the short-time component approximately an order of magnitude larger than that for the longer time component. The latter rate constant agrees with that of Rice-Ramsperger-Kassel-Marcus (RRKM) theory, consistent with rapid intramolecular vibrational energy redistribution (IVR) and intrinsic RRKM dynamics for the Na+(Bz)2∗ cluster. A coupled phase space model was used to analyze the biexponential dissociation probability.