Journal ArticleDOI
Kinetic origin of the ozone isotope effect: a critical analysis of enrichments and rate coefficients
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TLDR
In this article, the rate coefficients of ozone formation O + O2======→ O3 of about 50% characterizes the ozone isotope effect and demonstrates its kinetic origin and the rate coefficient correlates with the zero-point energy change of the oxygen molecules participating in the isotope exchange reactions but not with the mass of the ozone molecules.Abstract:
The oxygen isotope anomaly in ozone was first identified in isotopomers 49O3 and 50O3 with enrichments of over 10%. Recent rate coefficient measurements imply a new interpretation of the anomaly. The large variability of the rate coefficients of ozone formation O + O2
→ O3 of about 50% characterizes the ozone isotope effect and demonstrates its kinetic origin. Surprisingly, the rate coefficients correlate with the zero-point energy change of the oxygen molecules participating in the isotope exchange reactions but not with the mass of the ozone molecules. Rate coefficients of symmetric molecules depart from this linear relationship by about 20%.read more
Citations
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Journal ArticleDOI
History and applications of mass-independent isotope effects
TL;DR: The discovery of the first chemically produced mass-independent isotope effect in 1983 by Thiemens & Heidenreich opened a broad variety of applications, including physical chemistry studies, atmospheric chemistry, paleoclimatology, biologic primary productivity assessment, Solar System origin and evolution, planetary atmospheres (Mars), and the origin of life in Earth's earliest environment.
Journal ArticleDOI
Quantum dynamics of complex-forming bimolecular reactions
TL;DR: The reaction path for a complex-forming reaction is often barrierless, which results in weak and sometimes negative temperature dependence for its rate constant, and the product angular and internal distributions of such reactions also bear clear signatures as mentioned in this paper.
Journal ArticleDOI
Isotope effects in the chemistry of atmospheric trace compounds.
Carl A. M. Brenninkmeijer,Christof Janssen,Jan Kaiser,Thomas Röckmann,T. S. Rhee,Sergey Assonov +5 more
Journal ArticleDOI
The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface
Rüdiger Siebert,Paul Fleurat-Lessard,Reinhard Schinke,Martina Bittererová,Stavros C. Farantos +4 more
TL;DR: In this article, an ab initio potential energy surface for the ground electronic state of ozone is presented, which covers the three identical C2v (open) minima, the D3h (ring) minimum, as well as the O(3P)+O2(3Σg−) dissociation threshold.
Journal ArticleDOI
DYNAMICAL STUDIES OF THE OZONE ISOTOPE EFFECT: A Status Report
TL;DR: The focus is the intriguing isotope dependence of the recombination rate coefficient as observed by Mauersberger and coworkers in the last decade, and the results of these investigations of the ozone kinetics are discussed.
References
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Journal ArticleDOI
Strange and unconventional isotope effects in ozone formation.
Yi Qin Gao,Rudolph A. Marcus +1 more
TL;DR: In this article, an RRKM (Rice, Ramsperger, Kassel, and Marcus) based theory was used to treat both effects and to calculate the isotope effects consistent with a wide array of experimental results.
Journal ArticleDOI
Ozone isotope enrichment: isotopomer-specific rate coefficients
TL;DR: Six rate coefficients of relative ozone formation contradict the role of molecular symmetry in the process that results in the enrichment of heavy ozone isotopomers and suggest the observed isotope effect for each isotopomer may be caused by the preponderance of a single reaction channel and not through molecular symmetry selection.
Journal ArticleDOI
Laboratory studies of heavy ozone
TL;DR: The ozone produced was found to be enriched in both of its heavy isotopes, and the results of this experiment have clearly isolated the source of the isotope effect to the gas phase O({sup 3}P) + O{sub 2}(sup 3 {Sigma}{sub g}) recombination reaction as discussed by the authors.
Journal ArticleDOI
Temperature and pressure dependence of ozone formation rates in the range 1-1000 bar and 90-370 K
H. Hippler,R. Rahn,J. Troe +2 more
TL;DR: In this paper, the authors studied the recombination O+O2+M→O3+M in the bath gases M=He, Ar, and N2 over the temperature range 90-370 K and the pressure range 1-1000 bar.
Journal ArticleDOI
An intramolecular theory of the mass-independent isotope effect for ozone. I
B. C. Hathorn,Rudolph A. Marcus +1 more
TL;DR: In this article, an intramolecular theory of the unusual mass-independent isotope effect for ozone formation and dissociation is described, in contrast with the massindependent effect observed for scrambled mixtures.
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