This paper presents an overview of recent progress in spectroscopic studies of the energetic nitroimine 4,6-bis(nitroimino)-1,3,5-triazinan-2-one (DNAM), based on experimental and theoretical data. The following topics are considered: variable temperature FTIR spectroscopy (4000−400 cm-1) applied to the study of natural and isotopically substituted (deuterated) samples aiming to obtain a successful vibrational assignment of the spectra and to investigate H-bonding interactions; extensive theoretical work based on accurate quantum chemical calculations (ab initio MP2 and DFT/B3LYP; harmonic and anharmonic vibrational calculations) to model and help interpreting the experimental findings, as well as to provide fundamental data on this simple prototype nitroimine that can be used as a starting point to the study of more complex related compounds. This work allowed us to reveal detailed features of the IR spectrum of the title compound, presenting, for the first time, plausible assignments. ; http://dx.doi.org/10.1021/jp711153g