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Spectroscopy of OSSO and Other Sulfur Compounds Thought to be Present in the Venus Atmosphere

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2020, 124, 35, 7047-7059
    A: Spectroscopy, Molecular Structure, and Quantum Chemistry

    Spectroscopy of OSSO and Other Sulfur Compounds Thought to be Present in the Venus Atmosphere
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2020, 124, 35, 7047–7059
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    https://doi.org/10.1021/acs.jpca.0c04388
    Published August 11, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The spectroscopy of cis-OSSO and trans-OSSO is explored and put into the context of the Venusian atmosphere, along with other sulfur compounds potentially present there, namely, S2O, C1-S2O2, trigonal-S2O2, and S3. UV–vis spectra were calculated using the nuclear ensemble approach. The calculated OSSO spectra are shown to match well with the 320–400 nm near-UV absorption previously measured on Venus, and we discuss the challenges of assigning OSSO as the Venusian near-UV absorber. The largest source of uncertainty is getting accurate concentrations of sulfur monoxide (3SO) in the upper cloud layer of Venus (60–70 km altitude) since the 3SO self-reaction is what causes cis- and trans-OSSO to form. Additionally, we employed the matrix-isolation technique to trap OSSO formed by microwave discharging a gas mixture of argon and SO2 and then depositing the mixture onto a cold window (6–12 K). Anharmonic vibrational transition frequencies and intensities were calculated at the coupled cluster level to corroborate the matrix-isolation FTIR spectra. The computationally calculated UV–vis and experimentally recorded IR spectra presented in this work aid future attempts at detecting these sulfur compounds in the Venusian atmosphere.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c04388.

    • Details on the UV–vis spectral calculations including validation of the method with SO2 as the test molecule; a linear y-axis version of Figure 2; details on how the relative OSSO isomer populations were obtained; a detailed description of the full-dimensionality local mode model used to calculate vibrational frequencies and intensities for the OSSO isomers; additional output from the calculations of vibrational transition frequencies and intensities; supplementary spectra from the matrix-isolation IR spectroscopy experiments; additional details on the rate constant for the 3SO +3SO reaction to form OSSO; details on how the formation rate of 3SO from the photochemistry of SO2 was calculated (PDF)

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    Cited By

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    This article is cited by 18 publications.

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    18. Y. J. Lee, A. García Muñoz, A. Yamazaki, M. Yamada, S. Watanabe, T. Encrenaz. Investigation of UV Absorbers on Venus Using the 283 and 365 nm Phase Curves Obtained From Akatsuki. Geophysical Research Letters 2021, 48 (7) https://doi.org/10.1029/2020GL090577
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2020, 124, 35, 7047–7059
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.0c04388
    Published August 11, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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