Description of the Methylene Amidogene Radical and Its Anion with an Economical Treatment of Correlation Effects...

The ground and low-lying excited state electronic structural properties (such as equilibrium geometries, harmonic frequencies, excitation energies, barrier energy, and so on) of the methylene amidogene radical (H₂CN) and its anion (H₂CN^-) have been studied using the CASCI (complete active space configuration interaction) and SSMRPT (state-specific multireference Møller-Plesset perturbation theory) methods with density function theory (DFT) orbitals. Here, the span of the active orbitals have been obtained from Kohn-Sham DFT using B3LYP exchange-correlation functionals in the CASCI (DFT-CASCI) approximation to describe nondynamic correlation associated with electronic degeneracies. The DFT-SSMRPT protocol provides an attractive way to deal with both dynamical and nondynamical correlation effects in strongly correlated systems such as H₂CN and H₂CN^-. The present work clearly indicates that the electronic absorption band near 35,050 cm^-1 corresponds to the B̃²A₁ ← X̃²B₂ transition. DFT-SSMRPT findings are in close agreement with high-level theoretical estimates. It is concluded that the transition at 1725 cm^-1 could be due to the CN stretching of the trans-HCNH isomer which is originally assigned to the CN stretch of H₂CN in the experiment. The present results confirm most of the previous vibrational assignments. It is not possible to definitively assign a transition to the 35,600 cm^-1 band with the present estimations, suggesting further experiment is urgently called for.