Competition between the concerted and nonconcerted addition of ozone to a double bond

Krisyuk, B. E.; Maiorov, A. V.

doi:10.1134/s1990793111090065

Cited by 9 publications

(18 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This competition includes the switching between the mechanisms, affected by the various substituent effects. It is proposed that the Criegee mechanism predominates in the case of the reaction of ozone with ethylene , and other investigated alkenes, whereas the DeMore mechanism is favorable for tetrafluoroethylene and hexafluoropropylene . However, reliable data on the energy and activation barriers of the individual elementary steps and on the relative contribution of the mechanisms for alkenes and alkynes with different substituents to the net reaction are lacking so far.…”

Section: Introductionmentioning

confidence: 99%

“…The spin-restricted KS-DFT methods resulted in the detection of molecular TS1, whereas the application of spin-unrestricted KS-DFT gives both TS2 and TS1. Both transition states were described at one level by the B3LYP and PBE0 DFT methods, ab initio QCISD and CCSD methods, and by the MRMP2 method with geometry optimization performed with CASSCF and UMP2 methods . These theory levels do not account for static and dynamics electron correlation in a balanced way.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

et al. 2012

View full text Add to dashboard Cite

The mechanisms of the initial step in chemical reaction between ozone and ethylene were studied by multireference perturbation theory methods (MRMP2, CASPT2, NEVPT2, and CIPT2) and density functional theory (OPW91, OPBE, and OTPSS functionals). Two possible reaction channels were considered: concerted addition through the symmetric transition state (Criegee mechanism) and stepwise addition by the biradical mechanism (DeMore mechanism). Predicted structures of intermediates and transition states, the energies of elementary steps, and activation barriers were reported. For the rate-determining steps of both mechanisms, the full geometry optimization of stationary points was performed at the CASPT2/cc-pVDZ theory level, and the potential energy surface profiles were constructed at the MRMP2/cc-pVTZ, NEVPT2/cc-pVDZ, and CIPT2/cc-pVDZ theory levels. The rate constants and their ratio for reaction channels calculated for both mechanisms demonstrate that the Criegee mechanism is predominant for this reaction. These results are also in agreement with the experimental data and previous computational results. The structure of DeMore prereactive complex is reported here for the first time at the CCSD(T)/cc-pVTZ and CASPT2/cc-pVDZ levels. Relative stability of the complexes and activation energies were refined by single-point energy calculations at the CCSD(T)-F12/VTZ-F12 level. The IR shifts of ozone bands due to formation of complexes are presented and discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

et al. 2012

View full text Add to dashboard Cite

show abstract

“…58 However, certain features of ozonolysis via the Criegee mechanism 59 indicate that the Criegee and DeMore mechanisms can compete efficiently, as influenced by the presence of substituents around the olefinic bond. It is proposed that the Criegee mechanism predominates in the case of the reaction of ozone with ethene 59,60 and other studied alkenes, whereas the DeMore mechanism is preferred for tetrafluoroethene. 61 Our gas-phase calculations, which suggest a concerted ozone addition across isoprene double bonds, are consistent with the Criegee mechanism.…”

Section: ■ Resultsmentioning

confidence: 99%

Multiple Stable Isoprene–Ozone Complexes Reveal Complex Entrance Channel Dynamics in the Isoprene + Ozone Reaction

et al. 2020

View full text Add to dashboard Cite

Accurately characterizing isoprene ozonolysis continues to challenge atmospheric chemists. The reaction is believed to be a spontaneous, concerted cycloaddition. However, little information is available about the entrance channel and isoprene–ozone complexes thought to define the long-range portion of the reaction coordinate. Our coupled cluster and auxiliary field quantum Monte Carlo calculations predict multiple stable isoprene–ozone van der Waals complexes for trans-isoprene in the gas phase with moderate association energies. These results indicate that long-range dynamics in the isoprene–ozone entrance channel can impact the overall reaction in the troposphere and provide the spectroscopic information necessary to extend the microwave characterization of isoprene ozonolysis to prereactive complexes. At the air–water interface, Born–Oppenheimer molecular dynamics simulations indicate that the cycloaddition reaction between ozone and trans-isoprene follows a stepwise mechanism, which is quite distinct from our proposed gas-phase mechanism and occurs on a femtosecond time scale. The stepwise nature of isoprene ozonolysis on the aqueous surface is more consistent with the DeMore mechanism than with the Criegee mechanism suggested by the gas-phase calculations, suggesting that the reaction media may play an important role in the reaction. Overall, these predictions aim to provide a missing fundamental piece of molecular insight into isoprene ozonolysis, which has broad tropospheric implications due to its critical role as a nighttime source of hydroxyl radicals.

show abstract

“…1 Though studies throughout the years have proposed several alternatives for the reaction mechanism, the mechanism originally put forward by Criegee has been found to predominate. [2][3][4] In the Criegee mechanism, 5 the ozone molecule undergoes a concerted cycloaddition to a carbon-carbon double bond. The addition results in the breakage of the p bond between the carbon atoms and the concerted formation of two carbon-oxygen bonds that results in an unstable cyclic molozonide intermediate (the primary ozonide, or POZ).…”

Section: Introductionmentioning

confidence: 99%

“…Moving beyond benzene toward polycyclic aromatic hydrocarbons (PAH), Chu et al performed geometry optimizations and vibrational frequency calculations at the B3LYP/6-31G** level of theory for the addition of ozone to surface-adsorbed anthracene, pyrene, and benzo[a]pyrene. 16 The loss in planarity upon ozone addition as the C atoms undergoing reaction change hybridization from sp 2 to sp 3 was found to be an important factor in the determination of the reaction energy. In effect, the loss of planarity in PAHs that are adsorbed on a surface involves liftoff from the surface, which carries an energetic penalty.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions

Chapleski

Morris

Troya

2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We present an investigation of the reaction of ozone with C60 fullerene using electronic structure methods. Motivated by recent experiments of ozone exposure to a C60 film, we have characterized stationary points in the potential energy surface for the reactions of O3 with C60 that include both the formation of primary ozonide and subsequent dissociation reactions of this intermediate that lead to C-C bond cleavage. We have also investigated the addition of multiple O3 molecules to the C60 cage to explore potential reaction pathways under the high ozone flux conditions used in recent experiments. The lowest-energy product of the reaction of a single ozone molecule with C60 that results in C-C bond breakage corresponds to an open-cage C60O3 structure that contains ester and ketone moieties at the seam. This open-cage product is of much lower energy than the C60O + O2 products identified in prior work, and it is consistent with IR experimental spectra. Subsequent reaction of the open-cage C60O3 product with a second ozone molecule opens a low-energy reaction pathway that results in cage degradation via the loss of a CO2 molecule. Our calculations also reveal that, while full ozonation of all bonds between hexagons in C60 is unlikely even under high ozone concentration, the addition of a few ozone molecules to the C60 cage is favorable at room temperature.

show abstract

Competition between the concerted and nonconcerted addition of ozone to a double bond

Cited by 9 publications

References 21 publications

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

Multiple Stable Isoprene–Ozone Complexes Reveal Complex Entrance Channel Dynamics in the Isoprene + Ozone Reaction

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions

Contact Info

Product

Resources

About

Competition between the concerted and nonconcerted addition of ozone to a double bond

Cited by 9 publications

References 21 publications

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

Quantum Chemical Study of the Initial Step of Ozone Addition to the Double Bond of Ethylene

Multiple Stable Isoprene–Ozone Complexes Reveal Complex Entrance Channel Dynamics in the Isoprene + Ozone Reaction

A theoretical study of the ozonolysis of C60: primary ozonide formation, dissociation, and multiple ozone additions

Contact Info

Product

Resources

About

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions