Density functional study of nitrogen oxides

Abstract

Equilibrium geometries, bond dissociation energies, dipole moments, harmonic vibrational frequencies, and infrared intensities were calculated for a set of ten neutral nitrogen oxides (NO, NO2, NO3, N2O, sym N2O2, asym N2O3, sym N2O3, sym N2O4, asym N2O4, and N2O5) by applying one local and two gradient-corrected nonlocal functionals in a Gaussian-type-orbital density functional method. Comparison with available experimental data shows that, except for the bond dissociation energies, the local functional gives very accurate molecular properties. Nonlocal functionals considerably improve the bond dissociation energies, but the results still overestimate the experimental values by about 10 kcal/mol on average. For the other properties, the results obtained with nonlocal functionals are not necessarily superior to those calculated with the local functional. The properties of two molecules (sym N2O3 and asym N2O4) are predicted for the first time and several reassignments are proposed in the vibrational spectra of di-nitrogen oxides.