Symmetry-adapted-cluster configuration interaction (SAC-CI) wave functions were employed to compute 16 singlet and 13 triplet
vertical transitions, and 14 ionized states including relative intensities of the nitramide molecule, H
2NNO
2. This molecule is the simplest neutral closed-shell molecule which has an N–NO
2 bond and is a member of the nitramine family, R,R′N(NO
2), an important class of energetic materials with practical applications. The present nitramide results showed strong similarities
with the ones of the
N,
N-dimethylnitramine molecule, which has also an N–NO
2 bond and was previously studied using the SAC-CI method. Experimental ultraviolet and photoelectron band spectra of the nitramide
molecule could be successfully assigned. All the singlet transitions have valence character. The computed singlet and triplet
transitions, excepting a singlet one, result from excitation originating in the four highest occupied molecular orbitals,
which have close energies. Most of the singlet and triplet transitions involved mixing of singly excited configurations. The
strongest computed transition, at 6.8 eV, is a mixture of two
nπ
NO2 → π
* configurations corresponding to excitations from the highest occupied molecular orbital (HOMO) to the first two virtual orbitals
and has an optical oscillator strength value of 0.2665. The computed ionized states described the whole measured spectrum,
have excellent agreement when compared with the measured ionization potentials and revealed an inversion of the ordering of
the first states not expected according to Koopmanns’ theorem, thereby showing the limitations of the latter.
Keywords Nitramide, NH2NO2
- SAC-CI wave functions - Excited states - Ionized states - UV spectrum - Photoelectron spectra - Energetic materials