Theoretical investigation of the temperature dependence of the O+O2 exchange reaction

Fleurat‐Lessard, Paul; Grebenshchikov, Sergy Yu.; Siebert, Rüdiger; Schinke, Reinhard; Halberstadt, Nadine

doi:10.1063/1.1525255

Cited by 72 publications

(163 citation statements)

References 49 publications

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“…14 Experimental kinetics data suggest that the reaction path is barrier-less. 15,16 There were several attempts to determine the level of theory required to compute a better surface for O 3 .…”

Section: Introductionmentioning

confidence: 99%

Global permutationally invariant potential energy surface for ozone forming reaction

Ayouz

Babikov

2013

The Journal of Chemical Physics

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We constructed new global potential energy surface for O + O 2 → O 3 reaction. It is based on high level electronic structure theory calculations and employs fitting by permutationally invariant polynomial functions. This method of surface construction takes full advantage of permutation symmetry of three O nuclei and allows reducing dramatically the number of ab initio data points needed for accurate surface representation. New potential energy surface offers dramatic improvement over older surface of ozone in terms of dissociation energy and behavior along the minimum energy path. It can be used to refine the existing theories of ozone formation.

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Section: Introductionmentioning

confidence: 99%

Global permutationally invariant potential energy surface for ozone forming reaction

Ayouz

Babikov

2013

The Journal of Chemical Physics

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“…Yet a quantum mechanical characterization of the reaction dynamics is a necessity because of the importance of quantum effects such as zero-point energy and resonances in this system (14,15,17,19,20). These quantum effects render the conventional quasi-classical trajectory (QCT) results (21,22) quantitatively unreliable, although they may still provide valuable mechanistic insights.…”

Section: Resultsmentioning

confidence: 99%

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

Sun

Liu

Lin

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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The O þ O 2 exchange reaction is a prerequisite for the formation of ozone in Earth's atmosphere. We report here state-to-state differential and integral cross sections for several O þ O 2 isotopeexchange reactions obtained by dynamically exact quantum scattering calculations at collision energies relevant to atmospheric conditions. These reactions are shown to be highly nonstatistical, evidenced by dominant forward scattering and deviation of the integral cross section from the statistical limit. Mechanistic analyses revealed that the nonstatistical channel is facilitated by shortlived osculating resonances. The theoretical results provided an in-depth interpretation of a recent molecular beam experiment of the exchange reaction and shed light on the initial step of ozone recombination.complex-forming reactions | isotope effects | ozone | reactive scattering M ost chemical reactions need be activated to overcome the energy barrier, but many others require little or no activation because the intrinsic reaction path is barrierless (1). The latter type of reactions typically involves free radicals. Even at very low energies, their encounters lead to a relatively stable intermediate complex, which eventually breaks up to form products. Such complex-forming reactions are prevalent in interstellar clouds, in atmospheres, and in other gas-phase conditions such as combustion. The complex-forming mechanism manifests in various measurable attributes, such as a non-Arrhenius rate constant and a product angular distribution peaked in both forward and backward directions. exchange reaction is a prototypical complex-forming reaction via the metastable ozone (O Ã3 ) intermediate, supported by a ∼1.13 eV potential well (2). The importance of this reaction derives from the fact that it is a prerequisite for the formation of ozone in Earth's atmosphere (3, 4):in which the metastable ozone formed during the exchange reaction is stabilized by collisions with a third body (M). An in-depth understanding of the bimolecular isotope exchange reactions will not only advance our knowledge of complex-forming reactions in general, but also shed light on the surprising and significant enrichment of heavy ozone isotopomers discovered in the stratosphere (5) and in laboratory settings (6) more than 20 years ago. A key issue for a complex-forming reaction is whether it is statistical or not. If the reaction is dominated by a sufficiently longlived intermediate, the reactivity is completely determined by the availability of open channels at a given energy (7,8), and dynamics becomes unimportant. This simple statistical picture has been very successful in understanding many complex-forming reactions (9). On the other hand, ample examples can be found for nonstatistical complex-forming reactions (10-12), often due to the short lifetime of the so-called "osculating" intermediate complex (13).Recently, van Wyngarden et al. (11) reported an important crossed molecular beam study of the 16 O þ 36 O 2 → 34 O 2 þ 18 O exchange reaction at 0.32 eV of co...

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“…As discussed above, direct use of MRCI at that basis level substantially underestimates the dissociation energy, so an adjusted hybrid PES was constructed. 13 Schinke et al 4 were also aware of the sensitivity of the kinetics to the height of the pronounced reef found in their ab initio data and some numerical experiments were reported using versions of the PES in which the reef was removed. The low-lying vibrational levels on the SSB PES are very realistic matching experiment to a root-mean-squared error (RMSE) of ∼ 4 cm −1 for levels up to 4000 cm −1 above the ZPE.…”

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confidence: 99%

“…There is still a substantial discrepancy between predicted and observed low-temperature rates of O + O 2 isotope exchange. [1][2][3][4][5][6] Experimental rates are 3-5 times larger than predictions at low-temperature and exhibit a negative temperature dependence that has proven difficult to reproduce theoretically. Another outstanding issue of considerable ongoing interest is the anomalous isotope enrichment in atmospheric ozone, the so called mass-independent fractionation (MIF) effect.…”

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confidence: 99%

Communication: An accurate global potential energy surface for the ground electronic state of ozone

Dawes

Lolur

et al. 2013

The Journal of Chemical Physics

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Theoretical investigation of the temperature dependence of the O+O2 exchange reaction

Cited by 72 publications

References 49 publications

Global permutationally invariant potential energy surface for ozone forming reaction

Global permutationally invariant potential energy surface for ozone forming reaction

State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

Communication: An accurate global potential energy surface for the ground electronic state of ozone

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Theoretical investigation of the temperature dependence of the O+O2 exchange reaction

Cited by 72 publications

References 49 publications

Global permutationally invariant potential energy surface for ozone forming reaction

Global permutationally invariant potential energy surface for ozone forming reaction

State-to-state quantum dynamics of O + O 2 isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions

Communication: An accurate global potential energy surface for the ground electronic state of ozone

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State-to-state quantum dynamics of O + O ₂ isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions