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The electronic structure and spectroscopy of ClSOx (x = 1 and 2) isomers were investigated using coupled cluster theory and multireference interaction methods. In this study, the equilibrium geometry and harmonic vibrational frequencies of these isomers in their ground electronic state were shown. Our analysis of the vertical excitation energy and potential energy surface showed the photochemical instability of ClSO for wavelengths below 280 nm. Furthermore, the photodissociation of ClSO was unlikely to cause the formation of diatomic ClS. At the same time, ClSO could form atomic chlorine and SO as a result of photodissociation through the repulsive states. In the case of ClSO2, a novel weakly bound Cl–SO2 isomer was identified, indicating the potential influences on the chlorine and SO2 reactions. The potential energy surface of the most stable ClSO2 isomer also indicated the potential production of SO2 in both its ground and excited states. In addition, the electronic spectrum of ClSO2 was predicted to be broad, with numerous significant peaks in the near-UV‒Vis range. Valuable new insights into the chemical role of chlorine and sulfur in Venus's atmosphere were provided, along with a discussion of a potential mechanism contributing to the H2O and SO2 depletion in Venus's atmosphere. [ABSTRACT FROM AUTHOR]

Sulfur–chlorine cycles play a role in the atmosphere of Venus. It is thought that many sulfur–chlorine bearing molecules could be present in Venus's atmosphere and play an important role in its chemical processes. The goal of this work is to provide new insight into the electronic structure and spectroscopy of the [Cl, S, S, O] molecular system. Eight isomers could be formed, but only three were found to be thermodynamically stable relative to the first dissociation limit. We spectroscopically characterized the two lowest energy stable isomers, C1–ClSSO and trans-ClSSO, using the accurate CCSD(T)-F12/aug-cc-pVTZ method. The dipole moments of the two lowest energy stable isomers are predicted to be 1.90 and 1.60 debye, respectively. The C1–ClSSO isomer is suitable for laser induced fluorescence detection since the lowest excited electronic states absorb in the visible, ∼610 nm, and near UV region, 330 nm. We mapped the evolution of the low-lying excited electronic states along the ClS, SS, and SO bond lengths to find that the production of ClS, SO, or S2O is plausible, whereas the production of ClS2 is not allowed. [ABSTRACT FROM AUTHOR]

The electronic structure and spectroscopy of ClSOx (x = 1 and 2) isomers were investigated using coupled cluster theory and multireference interaction methods. In this study, the equilibrium geometry and harmonic vibrational frequencies of these isomers in their ground electronic state were shown. Our analysis of the vertical excitation energy and potential energy surface showed the photochemical instability of ClSO for wavelengths below 280 nm. Furthermore, the photodissociation of ClSO was unlikely to cause the formation of diatomic ClS. At the same time, ClSO could form atomic chlorine and SO as a result of photodissociation through the repulsive states. In the case of ClSO2, a novel weakly bound Cl-SO2 isomer was identified, indicating the potential influences on the chlorine and SO2 reactions. The potential energy surface of the most stable ClSO2 isomer also indicated the potential production of SO2 in both its ground and excited states. In addition, the electronic spectrum of ClSO2 was predicted to be broad, with numerous significant peaks in the near-UV‒Vis range. Valuable new insights into the chemical role of chlorine and sulfur in Venus's atmosphere were provided, along with a discussion of a potential mechanism contributing to the H2O and SO2 depletion in Venus's atmosphere., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)