Density functional calculations have been performed to describe reactions of ground-state 3d transition metal atoms (Sc-Ni) with N2O and NO2 molecules. From the analysis of the calculated reaction surfaces, a general reaction mechanism evolved. The reactions are initiated by electron transfer from metal to the oxidant molecule, which weakens the N-O bond and facilitates an O-(P-2) abstraction, 4s-3d hybridization taking place in the metal electronic structure plays an essential role in the net 4s(beta) electron transfer from the metal atom to the nitrogen-oxide molecule. These key steps contribute to connect the reactant and product channels on a single potential energy surface. The calculations revealed that reaction with NO2 yields stable oxo-nitrosyl insertion products, and their equilibrium structural properties can be understood by inspecting the 4pi(*) metal-oxide orbital occupancies. Correlation is obtained between the metal 3d ionization energies and the reaction rates as well as activation energies. This correlation provides additional support for the reaction mechanism called electron-transfer-assisted oxygen abstraction. This novel mechanism exhibits the basic features of the simple electron transfer and direct abstraction kinetic models and sheds new light on the so-called resonance interaction model as well.