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Strange and Unconventional Isotope Effects in Ozone Formation
Yi Qin Gao,R. A. Marcus*
The puzzling mass-independent isotopic enrichment in ozone
formation contrasts markedly with the more recently observed largeunconventional mass-dependent ratios of the individual ozone formationrate constants in certain systems. An RRKM (Rice, Ramsperger,Kassel,
Marcus)-based theory is used to treat both effects. Restrictionsof
symmetry on how energy is shared among the rotational/vibrationalstates of the ozone isotopomer, together with an analysis of thecompetition between the transition states of its two exit channels,permit the calculation of isotope effects consistent with a widearray
of experimental results.
Noyes Laboratory of Chemical Physics, Mail Code 127-72, California
Institute of Technology, Pasadena, CA 91125, USA.
*
To whom correspondence should be addressed. E-mail:
ram{at}caltech.edu
Abundance, Notation, and Fractionation of Light Stable Isotopes.
R. E. Criss and J. Farquhar (2008)
Reviews in Mineralogy and Geochemistry
68, 15-30
|Abstract »|Full Text »|PDF »
Mass-independent Oxygen Isotope Variation in the Solar Nebula.
E. D. Young, K. Kuramoto, R. A. Marcus, H. Yurimoto, and S. B. Jacobsen (2008)
Reviews in Mineralogy and Geochemistry
68, 187-218
|Abstract »|Full Text »|PDF »
Oxygen Isotopic Composition and Chemical Correlations in Meteorites and the Terrestrial Planets.
D. W. Mittlefehldt, R. N. Clayton, M. J. Drake, and K. Righter (2008)
Reviews in Mineralogy and Geochemistry
68, 399-428
|Abstract »|Full Text »|PDF »
The Oxygen Cycle of the Terrestrial Planets: Insights into the Processing and History of Oxygen in Surface Environments.
J. Farquhar and D. T. Johnston (2008)
Reviews in Mineralogy and Geochemistry
68, 463-492
|Abstract »|Full Text »|PDF »
Oxygen isotopic composition of carbon dioxide in the middle atmosphere.
M.-C. Liang, G. A. Blake, B. R. Lewis, and Y. L. Yung (2007)
PNAS
104, 21-25
|Abstract »|Full Text »|PDF »
Early evolution of atmospheric oxygen from multiple-sulfur and carbon isotope records of the 2.9 Ga Mozaan Group of the Pongola Supergroup, Southern Africa.
S. Ono, N. J. Beukes, D. Rumble, and M. L. Fogel (2006)
South African Journal of Geology
109, 97-108
|Abstract »|Full Text »|PDF »
Photochemical Mass-Independent Sulfur Isotopes in Achondritic Meteorites.
V. K. Rai, T. L. Jackson, and M. H. Thiemens (2005)
Science
309, 1062-1065
|Abstract »|Full Text »|PDF »
Presidential Address to the Mineralogical Society of America Seattle, November 4, 2003: A mineralogical and geochemical record of atmospheric photochemistry.
The terrestrial record of stable sulphur isotopes: a review of the implications for evolution of Earth's sulphur cycle.
J. Farquhar and B. A. Wing (2005)
Geological Society, London, Special Publications
248, 167-177
|Abstract »|PDF »
Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates.
M. F. Miller, I. A. Franchi, M. H. Thiemens, T. L. Jackson, A. Brack, G. Kurat, and C. T. Pillinger (2002)
PNAS
99, 10988-10993
|Abstract »|Full Text »|PDF »
Does Symmetry Drive Isotopic Anomalies in Ozone Isotopomer Formation?.
C. Janssen and R. A. Marcus (2001)
Science
294, 951a-951
|Full Text »|PDF »
