Beyond the established use of thermodynamic vs. kinetic control to explain chemical reaction selectivity, the concept of bifurcations on the potential energy surface (PES) is proving to be of pivotal importance with regard to selectivity. In this article we studied, by means of post-transition state (TS) direct dynamics simulations, the effect that vibrational and rotational excitation at the TS may have on the selectivity on a bifurcating PES. With this aim we studied the post-TS unimolecular reactivity of the [Ca(formamide)](2+) ion, for which Coulomb explosion and neutral loss reactions compete. The PES exhibits different kinds of non-intrinsic reaction coordinate (IRC) dynamics, among them PES bifurcations, which direct the trajectories to multiple reaction paths after passing the TS. The direct dynamics simulations were used to distinguish between the bifurcation non-IRC dynamics and non-IRC dynamics arising from atomistic motions directing the trajectories away from the IRC. Overall, we corroborated the idea that kinetic selectivity often does not reduce to a simple choice between paths with different barrier heights and instead dynamical behavior after passing the TS may be crucial. Importantly, rotational excitation may play a pivotal role on the reaction selectivity favoring non- thermodynamic products.