Spectroscopic Characterization of the First and Second Excited States of the HOSO Radical.

The spectroscopic properties of the ground and first two excited states of the HOSO radical are investigated using the internally contracted multireference configuration interaction method, including the Davidson correction (MRCI+Q) and explicit treatment of the electron correlation (MRCI-F12). The vertical and adiabatic excitation energies are also determined. The results reveal that both the 1 2A and 2 2A electronic states contain minima in their potential energy surfaces. The first excited state 1 2A possesses a nonplanar structure and has an adiabatic excitation energy of 1.45 eV (855 nm), lying in the near-infrared region. The second excited state 2 2A has a planar geometry and an adiabatic excitation energy of 2.91 eV (426 nm) existing in the visible region. The calculated oscillator strengths for the vertical electronic excitations to the 1 2A (327 nm) and 2 2A (270 nm) states are 0.003 and 0.022, respectively, indicating experimental intensity should be observed. The small but non-negligible Franck-Condon factors for excitations ∼300 nm, and the broad and intense absorption feature in the 225-275 nm region suggest that detection of the HOSO radical with electronic spectroscopy may be feasible.

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.