Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO[subscript 2] and the implications to the early earth's atmosphere
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Whitehill-2013-Vibronic origin of s.pdf
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Author(s)
Whitehill, Andrew Richard
Ono, Shuhei
Xie, Changjian
Hu, Xixi
Xie, Daiqian
Guo, Hua
Date Issued
July 2013
Journal
Proceedings of the National Academy of Sciences
Publisher
National Academy of Sciences (U.S.)
Citation
Whitehill, A. R., C. Xie, X. Hu, D. Xie, H. Guo, and S. Ono. “Vibronic Origin of Sulfur Mass-Independent Isotope Effect in Photoexcitation of SO2 and the Implications to the Early Earth’s Atmosphere.” Proceedings of the National Academy of Sciences 110, no. 44 (October 29, 2013): 17697–17702.
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Final published version
Abstract
Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ([superscript 16]O, [superscript 17]O, [superscript 18]O) and sulfur ([superscript 32]S, [superscript 33]S, [superscript 34]S, [superscript 36]S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ[superscript 33]S up to 78‰ and Δ[superscript 36]S up to 110‰, from the broadband excitation of SO[subscript 2] in the 250–350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO[subscript 2] ([~ over a][superscript 3]B[subscript 1]), which results from intersystem crossing from the excited singlet ([~ over A][superscript 1]A[subscript 2]/[~ over B][superscript 1]B[subscript 1]) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO[subscript 2] and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO[subscript 2] to the singlet states but from an isotope selective spin–orbit interaction between the singlet ([~ over A][superscript 1]A[subscript 2]/[~ over B][superscript 1]B[subscript 1]) and triplet ([~ over a][superscript 3]B[subscript 1]) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for [superscript 33]SO[subscript 2] and [superscript 36]SO[subscript 2] for the low vibrational levels of the [~ over A][superscript 1]A[subscript 2] state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.
MIT Department
Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
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DOI of Published Version
https://doi.org/10.1073/pnas.1306979110
