Energy surfaces of low-lying states of O3 and SO2

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Abstract
Density functional calculations have been performed for the energy surfaces of the ground states (x 1A1) and low‐lying excited states (1 3B1, 1 3B2, 1 1B1, 1 1B2) of O3 and SO2. Vertical excitation energies for the 1 3A2 and 1 1A2 states have also been calculated. The agreement with available experimental information is qualitatively better than for Hartree–Fock calculations and comparable to the predictions of configuration interaction calculations. Plots of the geometry dependence of the one‐electron eigenvalues (Walsh diagrams) give insight into the similarities and differences between the bonds in O3 and SO2. Calculations have also been performed for the ground state of SO. Dissociation energies in O2, O3, SO, and SO2 are overestimated by ∼2 eV, a consequence of the local density approximation used for the exchange‐correlation energy.