UV irradiation and infrared observation of sulfur dioxide clusters and solids at cryogenic temperature

Ito, Fumiyuki; Koga, Ryoichi; Negishi, Shun; Hirahara, Yasuhiro

doi:10.1016/j.cplett.2023.140742

Cited by 3 publications

(1 citation statement)

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“…Its chemistry is associated with the tropospheric formation of sulfuric acid, a constituent of acid rain and sulfate aerosols. − The triplet excited states of sulfur dioxide are accessed by near-UV solar radiation (with absorption band from 240 to 330 nm) and have a lifetime of 7.97 ± 1.7 × 10 –4 s, indicating that they are able to react with atmospheric trace gases. Indeed, the excited triplet states of sulfur dioxide have been shown to react with different species, − and the reaction of 3 SO 2 with H 2 O at the surface of water droplets constitutes a source of atmospheric sulfuric acid. ,− …”

Section: Introductionmentioning

confidence: 99%

Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃

Anglada,

Martins-Costa,

Francisco

et al. 2024

J. Am. Chem. Soc.

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The triplet excited states of sulfur dioxide can be accessed in the UV region and have a lifetime large enough that they can react with atmospheric trace gases. In this work, we report high level ab initio calculations for the reaction of the a3B1 and b3A2 excited states of SO2 with weak and strong acidic species such as HCOOH and HNO3, aimed to extend the chemistry reported in previous studies with nonacidic H atoms (water and alkanes). The reactions investigated in this work are very versatile and follow different kinds of mechanisms, namely, proton-coupled electron transfer (pcet) and conventional hydrogen atom transfer (hat) mechanisms. The study provides new insights into a general and very important class of excited-state-promoted reactions, opening up interesting chemical perspectives for technological applications of photoinduced H-transfer reactions. It also reveals that atmospheric triplet chemistry is more significant than previously thought.

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Section: Introductionmentioning

confidence: 99%

Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃

Anglada,

Martins-Costa,

Francisco

et al. 2024

J. Am. Chem. Soc.

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Mid-infrared imaging spectroscopic measurements of C2H4 frost simulating the outer solar system environments

Koga,

Negishi,

Zhao

et al. 2024

Earth Planets Space

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In the dense and cold atmosphere of Titan, the presence of C2H4 haze has been confirmed by the observations of spacecraft. In the present study, original cryogenic experimental equipment was developed to simulate the low-temperature solid formation of C2H4 in combination with in-situ infrared spectroscopic measurements. As a result, out-of-plane bending vibration ν7 of solid-phase C2H4 located at ~ 10.5 μm was successfully detected with high sensitivity, and two-dimensional spectrographs of C2H4 at low temperatures were obtained. The obtained spectra of C2H4 can be fitted to the double Lorentzian function with various heights, central wavelengths, and full widths at half the maximum (FWHM) of the two-component Lorentzian functions. They were classified into three types using the fitting parameters. However, their spectral shapes are different from the amorphous, metastable, and crystalline forms obtained by the previous laboratory experiment in terms of the distance of two peak wavelengths and FWHM. The results may link to understanding the spectral band properties of C2H4 condensation in the haze component of Titan. Graphical Abstract

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

Takahashi,

Ito,

Miyazaki

2024

Molecules

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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.

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UV irradiation and infrared observation of sulfur dioxide clusters and solids at cryogenic temperature

Cited by 3 publications

References 44 publications

Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃

Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃

Mid-infrared imaging spectroscopic measurements of C2H4 frost simulating the outer solar system environments

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

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UV irradiation and infrared observation of sulfur dioxide clusters and solids at cryogenic temperature

Cited by 3 publications

References 44 publications

Triplet State Radical Chemistry: Significance of the Reaction of 3SO2 with HCOOH and HNO3

Triplet State Radical Chemistry: Significance of the Reaction of 3SO2 with HCOOH and HNO3

Mid-infrared imaging spectroscopic measurements of C2H4 frost simulating the outer solar system environments

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

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Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃

Triplet State Radical Chemistry: Significance of the Reaction of ³SO₂ with HCOOH and HNO₃