Detection and structural characterization of nitrosamide H₂NNO: A central intermediate in deNO_x processes

The structure and bonding of H₂NNO, the simplest N-nitrosamine, and a key intermediate in deNO_x processes, have been precisely characterized using a combination of rotational spectroscopy of its more abundant isotopic species and high-level quantum chemical calculations. Isotopic spectroscopy provides compelling evidence that this species is formed promptly in our discharge expansion via the NH₂ + NO reaction and is collisionally cooled prior to subsequent unimolecular rearrangement. H₂NNO is found to possess an essentially planar geometry, an NNO angle of 113.67(5)°, and a N-N bond length of 1.342(3) Å; in combination with the derived nitrogen quadrupole coupling constants, its bonding is best described as an admixture of uncharged dipolar (H₂N-N=O, single bond) and zwitterion (H₂N⁺=N-O^-, double bond) structures. At the CCSD(T) level, and extrapolating to the complete basis set limit, the planar geometry appears to represent the minimum of the potential surface, although the torsional potential of this molecule is extremely flat.