scholarly journals High-precision spectroscopy of32S,33S, and34S sulfur dioxide: Ultraviolet absorption cross sections and isotope effects

2008 ◽  
Vol 113 (D17) ◽  
Author(s):  
Sebastian O. Danielache ◽  
Carsten Eskebjerg ◽  
Matthew S. Johnson ◽  
Yuichiro Ueno ◽  
Naohiro Yoshida
Keyword(s):  
Sulfur Dioxide ◽  
High Precision ◽  
Cross Sections ◽  
Isotope Effects ◽  
Ultraviolet Absorption ◽  
Precision Spectroscopy ◽  
Absorption Cross

scholarly journals Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC<sup>32</sup>S, OC<sup>33</sup>S, OC<sup>34</sup>S and O<sup>13</sup>CS: isotopic fractionation in photolysis and atmospheric implications

2011 ◽  
Vol 11 (19) ◽  
pp. 10293-10303 ◽  
Author(s):  
S. Hattori ◽  
S. O. Danielache ◽  
M. S. Johnson ◽  
J. A. Schmidt ◽  
H. G. Kjaergaard ◽  
...  
Keyword(s):  
Cross Sections ◽  
Carbonyl Sulfide ◽  
Isotopic Fractionation ◽  
High Energy ◽  
Ultraviolet Absorption ◽  
Absorption Cross ◽  
Rare Isotopes ◽  
Mass Dependent ◽  
Franck Condon ◽  
Energy Side

Abstract. We report measurements of the ultraviolet absorption cross sections of OC32S, OC33S, OC34S and O13CS from 195 to 260 nm. The OCS isotopologues were synthesized from isotopically-enriched elemental sulfur by reaction with carbon monoxide. The measured cross section of OC32S is consistent with literature spectra recorded using natural abundance samples. Relative to the spectrum of the most abundant isotopologue, substitution of heavier rare isotopes has two effects. First, as predicted by the reflection principle, the Gaussian-based absorption envelope becomes slightly narrower and blue-shifted. Second, as predicted by Franck-Condon considerations, the weak vibrational structure is red-shifted. Sulfur isotopic fractionation constants (33ε, 34ε) as a function of wavelength are not highly structured, and tend to be close to zero on average on the high energy side and negative on the low energy side. The integrated photolysis rate of each isotopologue at 20 km, the approximate altitude at which most OCS photolysis occurs, was calculated. Sulfur isotopic fractionation constants at 20 km altitude are (−3.7 ± 4.5)‰ and (1.1 ± 4.2)‰ for 33ε and 34ε, respectively, which is inconsistent with the previously estimated large fractionation of over 73‰ in 34ε. This demonstrates that OCS photolysis does not produce sulfur isotopic fractionation of more than ca. 5‰, suggesting OCS may indeed be a significant source of background stratospheric sulfate aerosols. Finally, the predicted isotopic fractionation constant for 33S excess (33E) in OCS photolysis is (−4.2 ± 6.6)‰, and thus photolysis of OCS is not expected to be the source of the non-mass-dependent signature observed in modern and Archaean samples.

Ultraviolet absorption cross sections of infrared laser excited UF6

1985 ◽  
Vol 83 (9) ◽  
pp. 4344-4347 ◽  
Author(s):  
K. C. Kim ◽  
S. M. Freund ◽  
M. S. Sorem ◽  
D. F. Smith
Keyword(s):  
Cross Sections ◽  
Infrared Laser ◽  
Ultraviolet Absorption ◽  
Absorption Cross

Near-infrared–ultraviolet absorption cross sections for Ge nanocrystals in SiO2 thin films: Effects of shape and layer structure

2011 ◽  
Vol 109 (9) ◽  
pp. 094314 ◽  
Author(s):  
Christian Uhrenfeldt ◽  
Jacques Chevallier ◽  
Arne Nylandsted Larsen ◽  
Brian Bech Nielsen
Keyword(s):  
Thin Films ◽  
Cross Sections ◽  
Near Infrared ◽  
Layer Structure ◽  
Ultraviolet Absorption ◽  
Absorption Cross ◽  
Ge Nanocrystals

scholarly journals Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC<sup>32</sup>S, OC<sup>33</sup>S, OC<sup>34</sup>S and O<sup>13</sup>CS: isotopic fractionation in photolysis and atmospheric implications

2011 ◽  
Vol 11 (7) ◽  
pp. 20487-20520 ◽  
Author(s):  
S. Hattori ◽  
S. O. Danielache ◽  
M. S. Johnson ◽  
J. A. Schmidt ◽  
H. G. Kjaergaard ◽  
...  
Keyword(s):  
Cross Sections ◽  
Carbonyl Sulfide ◽  
Isotopic Fractionation ◽  
High Energy ◽  
Ultraviolet Absorption ◽  
Absorption Cross ◽  
Rare Isotopes ◽  
Mass Dependent ◽  
Franck Condon ◽  
Energy Side

Abstract. We report measurements of the ultraviolet absorption cross sections of OC32S, OC33S, OC34S and O13CS from 195 to 260 nm. The OCS isotopologues were synthesized from isotopically-enriched elemental sulfur by reaction with carbon monoxide. The measured cross section of OC32S is consistent with literature spectra recorded using natural abundance samples. Relative to the spectrum of the most abundant isotopologue, substitution of heavier rare isotopes has two effects. First, as predicted by the reflection principle, the Gaussian-based absorption envelope becomes slightly more narrow and blue-shifted. Second, as predicted by Franck-Condon considerations, the weak vibrational structure is red-shifted. Sulfur isotopic fractionation constants (33ε, 34ε) as a function of wavelength are not highly structured, and tend to be close to zero on average on the high energy side and negative on the low energy side. Since OCS photolysis occurs in the lower stratosphere, the integrated photolysis rate of each isotopologue at 20 km was calculated. Sulfur isotopic fractionation constants at 20 km altitude are (−3.7 ± 4.5) ‰ and (1.1 ± 4.2) ‰ for 33ε and 34ε, respectively, which is inconsistent with the previously estimated large fractionation of over 73 ‰ in 34ε. This demonstrates that OCS photolysis does not produce sulfur isotopic fractionation of more than ca. 5 ‰, suggesting OCS may be the source of background stratospheric sulfate aerosols. Finally, the predicted isotopic fractionation constant for 33S excess (33E) in OCS photolysis is (−4.2 ± 6.6) ‰, and thus photolysis of OCS is not expected to be the source of the non-mass-dependent signature observed in modern and Archaean samples.

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