A classical trajectory simulation is performed to study the dynamics of Ne-atom scattering off an n-hexyl thiolate self-assembled monolayer (SAM). The energy distribution of the scattered Ne-atoms may be deconvoluted into a Boltzmann component based on the surface temperature and a remaining non- Boltzmann high energy component. The former component becomes as large as 100% at low Ne-atom incident energies and appears to assume a high incident energy asymptotic value of ~0.2-0.3 for incident angles less than 50. This Boltzmann component does not arise from a Ne-SAM intermediate, since the vast majority of the collisions are direct with only one inner turning point in the Ne + SAM motion. Instead, it has varying contributions from trajectories which directly scatter from and those that penetrate the SAM. The translation (T) → vibration (V) energy transfer mechanism for the former class of trajectories may have similarities to exit-channel T → V coupling in models of unimolecular dissociation. SAM penetration becomes more important as the initial translational energy E(i) is increased, resulting in both efficient and inefficient energy transfer. The latter results from repulsive forces as the Ne-atom is 'expelled' from the SAM. For incident angles less than 50°the size of the Boltzmann component scales with the total incident energy E1 reflecting equivalent energy transfer probabilities from the normal and parallel components of E1. Such a result is consistent with the corrugated SAM surface. Penetration of the SAM scales with the normal component of E1 for small incident angles θ(i) and E(i). Both the Boltzmann component to the transitional energy distribution of the scattered Ne atom, P(E(i)) and SAM penetration become negligible for an increase in θ(i) from 45°to 60°, suggesting an abrupt transition in the collision dynamics. The angular distributions for the scattered Ne-atoms are random for low initial energies E(i) and θ(i), reflecting the surface corrugation and not the presence of an actual Ne-SAM intermediate. At high E(i) and θ(i) the scattering is non- random, preferring to remain in the incident plane with the parallel component of E(i) conserved. This study shows there are ambiguities in associating a trapping desorption intermediate with statistical gas-surface scattering attributes, such as a Boltzmann component, in the translational energy distribution and a random angular distribution.