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Cyclic step-catalysis enables intermittent, atmospheric ammonia production, and can be integrated with sustainable and renewable energy sources. By employing metal (e.g., Mn) nitride, a nitrogen carrier, the rate-limiting N2 activation step is bypassed. In this work, molecular-level pathways, describing the reduction of Mn4N by dissociatively adsorbed hydrogen, were investigated using periodic density functional theory (DFT). The established mechanism confirmed that Fe and Ni doped in the nitride sublayer and top layer can disturb local electronic structures and be exploited to tune the ammonia production activity. The strength of N−M (M = Mn, Fe, Ni) and H−M bonds both determine the overall reduction thermochemistry. DFT-based modeling further showed that the low concentration of Fe or Ni in the Mn4N sublayer facilitates N diffusion by lowering the diffusion energy barrier. Also, these heteroatom dopant species, particularly Ni, decrease the reduction endergonicity, thanks to the strong hydrogen binding with the surface Ni dopant. The Brønsted−Evans−Polanyi relationship and linear scaling relationships have been developed to reveal ammonia evolution kinetic and energetic trends for a series of idealized Fe- and Ni-doped Mn4N. Deviations from the linear scaling relationship have been observed for certain doped systems, indicating potentially more complex behaviors of metal nitrides and intriguing promises for greater ammonia synthesis materials design opportunities.