Photoreactions of the C₂H₄–SO₂ Complex in a Low-Temperature Matrix Investigated by Infrared Spectroscopy and Density Functional Theory Calculations

Abstract

Ethylene and sulfur dioxide molecules were co-deposited on a CsI window at cryogenic temperature, and the photoproducts upon UV irradiation were observed using Fourier transform infrared (FTIR) spectroscopy. The products were found to be UV wavelength-dependent; at shorter wavelengths (λ = 266 nm) one strong peak was observed while more than three peaks were identified at longer UV wavelengths (λ = 300 nm). Spectral features changed seamlessly along with UV wavelength. Density functional theory (DFT) calculations were carried out for potential products, and spectral matches between observations and calculations seemed satisfactory, assuming a cyclic molecule (oxathietane 2-oxide) as the main photoproduct at longer UV wavelengths. On the other hand, the spectra of photoproducts at shorter UV wavelengths were reproduced by assuming the decomposition products of an intermediate, from the supplementary experiments using deuterated samples. Plausible photoreaction schemes were presented to account for the observed photoproducts.

Keywords

• ethylene
• sulfur dioxide
• photolysis
• matrix isolation
• infrared spectroscopy
• density functional calculation