Structures and vibrational frequencies of NaO₃ and NaO₃⁺: the ionization energy of NaO₃

Lee, Edmond P.F. and Wright, Timothy G. (2004) Structures and vibrational frequencies of NaO₃ and NaO₃⁺: the ionization energy of NaO₃. Journal of Physical Chemistry A, 108 (21), 4792-4798. (doi:10.1021/jp0490655).

Abstract

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(X^~2B₁) and NaO₃⁺(X^~1A₁). In both cases, a C-2v, 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.

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