Toward the observation of quartet states of the ozone radical cation: Insights from coupled cluster theory

• Published in: The Journal of chemical physics 2008-06, Vol.128 (21), p.214302-214302-12
• Main Authors: Speakman, Lucas D., Turney, Justin M., Schaefer, Henry F.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.2924128

Since the discovery of ozone depletion, the doublet electronic states of the ozone radical cation have received much attention in experimental and theoretical investigations, while the low-lying quartet states have not. In the present research, viable pathways to the quartet states from the lowest three triplet states of ozone, A 2 3 , B 2 3 , and B 1 3 , and excitations from the A 1 2 and B 2 2 states of the ozone radical cation have been studied in detail. The potential energy surfaces, structural optimizations, and vibrational frequencies for several states of ozone and its radical cation have been thoroughly investigated using the complete active space self-consistent field, unrestricted coupled cluster theory from a restricted open-shell Hartree-Fock reference including all single and double excitations (UCCSD), UCCSD method with the effects of connected triple excitations included perturbatively, and unrestricted coupled cluster including all single, double, and triple excitations with the effects of connected quadruple excitations included perturbatively. These methods used Dunning's correlation-consistent polarized core-valence basis sets, cc - pCV X Z ( X = D , T, Q, and 5). The most feasible pathways (symmetry and spin allowed transitions) to the quartet states are A 1 4 ← A 2 3 , A 2 4 ← A 2 3 , A 1 4 ← B 2 3 , A 2 4 ← B 1 3 , B 2 4 ← B 1 3 , A 2 4 ← A 1 1 , B 2 4 ← A 1 1 , and A 1 4 ← A 1 1 with vertical ionization potentials of 12.46, 12.85, 12.82, 12.46, 12.65, 13.43, 13.93, and 14.90 eV , respectively.