Excited electronic and ionized states of the nitramide molecule, H2NNO2, studied by the symmetry-adapted-cluster configuration interaction method

Abstract

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, H2NNO2. This molecule is the simplest neutral closed-shell molecule which has an N–NO2 bond and is a member of the nitramine family, R,R′N(NO2), 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–NO2 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 nπNO2 → 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.