Photochemistry from low-lying states of HOSO

Using configuration interaction ab initio methods, the evolution of the lowest electronic states of singlet and triplet spin multiplicities of HOSO⁺ along the stretching and bending coordinates of is investigated. Equilibrium geometries, rotational constants, and harmonic vibrational frequencies of the lowest electronic states are calculated, i.e., X¹A', 1¹A″, 1³A', and 1³A″. The global minimum of the 1¹A″ state is located below the first dissociation limit and its calculated lifetime is predicted to be 0.40 µs, making it suitable for detection by laser-induced fluorescence. According to the potential energy surfaces, HOSO⁺ should produce SO₂ ⁺ and H after ultraviolet photon absorption to the 2¹A' state. This work opens the door to investigate the branching ratio and the production rates of SO₂ ⁺, SO⁺, and OH from HOSO⁺. These insights can help understand the SO₂ cycle in the earth's atmosphere and its effect on cooling our planet.