Structures and Vibrational Frequencies of NaO3 and NaO3 +:  The Ionization Energy of NaO3

We use high-level ab initio, up to RCCSD(T), and the density functional theory (DFT) method, B3LYP, to obtain the geometry, vibrational frequencies, and heats of formation of NaO3(X̃2B1) and NaO3 +(X̃A1). In both cases, a C 2 v diamond structure is deduced. These values allow us also to derive the adiabatic ionization energy. We obtain the following values: ΔH f[NaO3,0K] = −13 ± 2 kcal mol-1, ΔH f[NaO3 +,0K] = 167 ± 2 kcal mol-1, and AIE(NaO3) = 7.80 ± 0.05 eV. In addition, it was found that the B3LYP functional performs very well for the O3 - species: both geometry and vibrational frequencies. For O3, the method performed well for the geometry, but not so well for the vibrational frequencies. Comparison is made where appropriate to experimental data and to previous calculations. Finally, ΔH r is calculated for a range of reactions that may contribute to the formation of NaO3 or NaO3 + in the atmosphere.