Geometries and energies of the excited states of O3 from ab initio potential energy surfaces

The geometries and relative energies of the nine lowest states of the ozone molecule have been determined in C2v symmetry from ab initio configuration interaction calculations in a [3s2p1d] contracted Gaussian basis. Calculations were carried out over a two‐dimensional grid of points in C2v symmetry to locate the optimum geometrical parameters R and ϑ for each state. For the ground 1A1 state the calculated properties (with experimental values in parentheses) are as follows: Re=1.299 A (1.271 A), ϑe=116.0° (116.8°), ω1=1235 cm−1 (1110 cm−1) and ω2=707 cm−1 (705 cm−1). Of the excited states only the lowest 3B2 state is found to have an adiabatic excitation energy (0.92 eV) less than the dissociation energy (De=1.13 eV) and hence to be a likely bound species. The 1B2 state responsible for the strong absorption in the Hartley band (4.7–5.8 eV) is stabilized by asymmetric distortions away from its equilibrium C2v geometry (Re=1.405 A, ϑe=108°) suggesting unequal bond lengths for this state or else purely disso...

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