Translational spectroscopy and coincidence detection of the neutral photofragments have been used to observe the dissociation dynamics of highly excited neutrals produced by charge exchange between keV cation beams with Cs, and the results from two novel systems are presented. CH₅ is formed slightly above the 3s Rydberg level and dissociates into two possible fragmentation channels, H loss and H₂ loss. The kinetic energy release distributions of the two products are presented and the branching ratio between the two is found to be 11.4 ± 1.5 : 1 with the H loss being the dominant channel. Production of the highly symmetric azabenzene sym-triazine in its 3s Rydberg state has been shown to induce dissociation to 3 HCN(Σ⁺). Examination of momentum correlation in the dissociation products shows that this dissociation occurs by two distinct mechanisms. Evidence from Monte Carlo simulations suggest a sequential mechanism occurs creating products accompanied by a kinetic energy release of ~1.5–5 eV. A symmetric concerted mechanism is also observed and is associated with products receiving a 2–4 eV kinetic energy release.