Multi-isotope study of fractionation effects in the ozone formation process

Wolf, Sophie; Bitter, Mark; Krankowsky, D.; Mauersberger, K.

doi:10.1063/1.1305890

Cited by 23 publications

(15 citation statements)

References 13 publications

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“…In the limit of negligible consumption of molecular oxygen and assuming that ozone destruction is insignificant, the isotopologue enrichment is directly linked to the rates of ozone formation and to the equilibrium constant K of exchange (): It should be noted that the enrichment is completely determined in terms of thermodynamic and kinetic quantities and independent of the molecular bath gas composition, as long as ozone production is low. This is in complete agreement with experimental observation [ Wolf et al , 2000]. Such a conclusion and analysis, however, must be questioned when, in a closed system, oxygen is quantitatively converted into ozone.…”

Section: Kinetic Considerationssupporting

confidence: 88%

Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)

Janssen

2005

J. Geophys. Res.

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O-containing ozone, is an essential feature of the unusual oxygen isotope effect in ozone formation. Whereas information on r 49 is sparse and of limited accuracy, precision in laboratory measurements of r 50 has recently been improved. The two most recent experiments, however, disagree on whether there is a preference for the formation of asymmetric over symmetric molecules or not (r 50 > 2 versus r 50 = 2). To throw light on this discrepancy, the temperature dependence of r 50 has been derived from a reanalysis of existing measurements: r 50 is found to decrease from 2.13 at 360 K to about 2.00 at 170 K. Kinetic model calculations show that the discrepancy between the two measurements disappears when temperature conditions for ozone formation are accounted for.

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Section: Kinetic Considerationssupporting

confidence: 88%

Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)

Janssen

2005

J. Geophys. Res.

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“…12͒. Measured enrichments 93 and reaction rate constant ratios 18 are also displayed for completeness on experimental data available on the overall process of ozone formation ͑1͒ but cannot directly be used for comparison here with present calculated ratios. It can be seen that the rate constants are sensitive to isotopes although the ratios do not follow any definite scaling rule as the isotope mass increases, and hence the deactivation rate constant for the formation of ozone is not indexed to the overall isotopic mass of molecule XY-Z.…”

Section: Resultsmentioning

confidence: 99%

Quantum-mechanical calculations on termolecular association reactions XY+Z+M→XYZ+M: Application to ozone formation

Charlo

Clary

2002

The Journal of Chemical Physics

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Articles you may be interested inFrozen rotor approximation in the mixed quantum/classical theory for collisional energy transfer: Application to ozone stabilization Towards quantum mechanical description of the unconventional mass-dependent isotope effect in ozone: Resonance recombination in the strong collision approximationWe present a quantum-mechanical model for termolecular association reactions XYϩZϩM→XYZϩM involving the formation of a long-lived complex XYZ*. The rotation of the molecule XYZ is treated in the infinite order sudden approximation ͑IOS͒ and its vibrations are treated by the coupled-channel method ͑VCC͒. Resonances featuring the XYZ* long-lived complex formation are first computed by means of the stabilization method and are then included in the vibrational basis functions used for the inelastic VCC-IOS scattering calculation. The method yields rate constants for the association process selected in resonance and bound states of XYZ. We apply the method to the formation of ozone and investigate isotope effects. Calculations of energy transfer and collision-induced recombination of OϩO 2 in collision with Ar are reported for a range of ozone isotopomers. The bending mode of O 3 is not treated explicitly in these computations. The results establish a strong selectivity in vibrational state-to-state cross sections for the deactivation of O 3 during the collisional energy transfer process with Ar. The present calculations also account for the high sensitivity of rate constants with respect to the isotopic composition of ozone molecules but not in the same proportion as experiments. The energy transfer from selected initial vibrational states is also calculated as a function of the initial relative kinetic energy.

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“…It also has been investigated in numerous laboratory experiments. [9][10][11][12] For a recent review of isotope effects see Ref. 13.…”

Section: Introductionmentioning

confidence: 99%

The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface

Siebert¹,

Fleurat‐Lessard²,

Schinke³

et al. 2002

The Journal of Chemical Physics

171

215

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New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy rangeWe present an ab initio potential energy surface for the ground electronic state of ozone. It is global, i.e., it covers the three identical C 2v ͑open͒ minima, the D 3h ͑ring͒ minimum, as well as the O( 3 P)ϩO 2 ( 3 ⌺ g Ϫ ) dissociation threshold. The electronic structure calculations are performed at the multireference configuration interaction level with complete active space self-consistent-field reference functions and correlation consistent polarized quadruple zeta atomic basis functions. Two of the O-O bond distances, R 1 and R 2 , and the O-O-O bending angle are varied on a regular grid ͑ca. 5000 points with R 1 уR 2 ). An analytical representation is obtained by a three-dimensional cubic spline. The calculated potential energy surface has a tiny dissociation barrier and a shallow van der Waals minimum in the exit channel. The ring minimum is separated from the three open minima by a high potential barrier and therefore presumably does not influence the low-temperature kinetics. The dissociation energy is reproduced up to 90% of the experimental value. All bound states of nonrotating ozone up to more than 99% of the dissociation energy are calculated using the filter diagonalization technique and employing Jacobi coordinates. The three lowest transition energies for 16 O 3 are 1101.9 cm Ϫ1 ͑1103.14 cm Ϫ1 ͒, 698.5 cm Ϫ1 ͑700.93 cm Ϫ1 ͒, and 1043.9 cm Ϫ1 ͑1042.14 cm Ϫ1 ͒ for the symmetric stretch, the bending, and the antisymmetric stretch modes, respectively; the numbers in parentheses are the experimental values. The root-mean-square error for all measured transition energies for 16 O 3 is only 5 cm Ϫ1 . The comparison is equally favorable for all other isotopomers, for which experimental frequencies are available. The assignment is made in terms of normal modes, despite the observation that with increasing energy an increasing number of states acquires local-mode character. At energies close to the threshold a large fraction of states is still unambiguously assignable, particularly those of the overtone progressions. This is in accord with the existence of stable classical periodic orbits up to very high energies.

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Multi-isotope study of fractionation effects in the ozone formation process

Cited by 23 publications

References 13 publications

Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)

Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)

Quantum-mechanical calculations on termolecular association reactions XY+Z+M→XYZ+M: Application to ozone formation

The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface

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Multi-isotope study of fractionation effects in the ozone formation process

Cited by 23 publications

References 13 publications

Intramolecular isotope distribution in heavy ozone (16O18O16O and 16O16O18O)

Intramolecular isotope distribution in heavy ozone (16O18O16O and 16O16O18O)

Quantum-mechanical calculations on termolecular association reactions XY+Z+M→XYZ+M: Application to ozone formation

The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface

Contact Info

Product

Resources

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Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)

Intramolecular isotope distribution in heavy ozone (¹⁶O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O)