Quantum chemistry investigations have been performed to study the gas-phase chemistry active during the MOVPE of GaN when Ga(CH3)(3) and NH3, diluted in a H2 carrier gas, are used as precursors. Optimized molecular geometries, energies, and transition-state structures of gas-phase species have been determined with density functional theory at the B3LYP/6-311+g(d,p) level. On the basis of the similarity with the soot formation mechanism active during hydrocarbon combustion, we propose that in this system a gas-phase chemistry is active and its reactivity is enhanced by a radical chain mechanism started from methyl radicals. Initiation reactions are surface processes or the pyrolysis of Ga(CH3)(3). A propagation mechanism composed of fast radical reactions, most of which without an activation energy, was identified, and kinetic constants were determined for each step. The proposed mechanism is able to describe the formation of large GaN adducts formed by up to three R-Ga-NH units. These molecules can give fast cyclization reactions that lead to the formation of six-membered cyclic species, which, similar to benzene for combustion, are thermodynamically stable in vast temperature and pressure ranges and can thus be considered as the first GaN nuclei. We also found that the presence of H2 as a carrier gas can greatly enhance the rate of formation of gas-phase particles because it is a major source of atomic hydrogen, a promoter of gas-phase reactivity.