Resonance enhanced multiphoton ionization and cavity ring down spectroscopies have been used to provide spatially resolved measurements of relative H atom and CH3 radical number densities, and NH column densities, in a hot filament (HF) reactor designed for diamond chemical vapor deposition and here operating with a 1% CH4/n/H-2 gas mixture-where n represents defined additions of N-2 or NH3. Three-dimensional modeling of the H/C/N chemistry prevailing in such HF activated gas mixtures allows the relative number density measurements to be placed on an absolute scale. Experiment and theory both indicate that N-2 is largely unreactive under the prevailing experimental conditions, but NH3 additions are shown to have a major effect on the gas phase chemistry and composition. Specifically, NH3 additions introduce an additional series of "H-shift" reactions of the form NHx+Hreversible arrowNH(x-1)+H-2 which result in the formation of N atoms with calculated steady state number densities >10(13) cm(-3) in the case of 1% NH3 additions in the hotter regions of the reactor. These react, irreversibly, with C-1 hydrocarbon species forming HCN products, thereby reducing the concentration of free hydrocarbon species (notably CH3) available to participate in diamond growth. The deduced reduction in CH3 number density due to competing gas phase chemistry is shown to be compounded by NH3 induced modifications to the hot filament surface, which reduce its efficiency as a catalyst for H-2 dissociation, thus lowering the steady state gas phase H atom concentrations and the extent and efficiency of all subsequent gas phase transformations. (C) 2002 American Institute of Physics.