A great deal of attention has been given to the decomposition chemistry of halons (halomethanes) due to their role in stratospheric ozone depletion. Knowledge of certain aspects of dissociation of halons such as the competition between radical and molecular pathways and their mechanistic details is limited. Halon molecules can isomerize to an iso form containing a halogen-halogen bond and such iso-halon forms have been identified as intermediates in condensed phase chemistry. Recently, a quantum chemistry study of role of isohalons in the gas phase decomposition of halomethanes has been reported. In the present work, we have investigated the ground state dissociation chemistry of select halon molecules - CF2Cl2, CF2Br2, CHBr3, and CH2BrCl using electronic structure theory calculations and direct chemical dynamics simulations. Classical trajectories were generated on-the-fly using density functional PBE0/6-31G* level of theory at a fixed total energy. Simulation results showed that molecular products, in general, were dominant for all the four molecules at the chosen energy. A variety of mechanisms such as direct dissociation via multicenter transition states, decomposition via isomerization, radical recombinations, and roaming pathways contributed to the formation of molecular products. Atomic level mechanisms are presented, and the role of iso-halons in the gas phase chemistry of halomethanes is clearly established.