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. 2018 Feb 28;3(2):2417-2427.
doi: 10.1021/acsomega.7b02002.

Hydration and Secondary Ozonide of the Criegee Intermediate of Sabinene

Mansour H Almatarneh  1   2 , Ismael A Elayan  1 , Mohammednoor Altarawneh  3 , Joshua W Hollett  4
Affiliations

Hydration and Secondary Ozonide of the Criegee Intermediate of Sabinene

Mansour H Almatarneh et al. ACS Omega. .

Abstract

A computational study of the formation of secondary ozonide (SOZ) from the Criegee intermediates (CIs) of sabinene, including hydration reactions with H2O and 2H2O, was performed. All of the geometries were optimized at the B3LYP and M06-2X with several basis sets. Further single-point energy calculation at the CCSD(T) was performed. Two major pathways of SOZ formation suggest that it is mainly formed from the sabinene CI and formaldehyde rather than sabina ketone and formaldehyde-oxide. However, in both pathways, the activation energies are within a range of ±5 kJ mol-1. Furthermore, the hydration reactions of the anti-CI with H2O and 2H2O showed that the role of the second water molecule is a mediator (catalyst) in this reaction. The dimer hydration reaction has lower activation energies than the monomer by 60 and 69 kJ mol-1, at the M06-2X/6-31G(d) and CCSD(T)+CF levels of the theory, respectively. A novel water-mediated vinyl hydroperoxide (VHP) channel from both the monomer and dimer has been investigated. The results indicate that the direct nonmediated VHP formation and dissociation is interestingly more possible than the water-mediated VHP. The density functional theory calculations show that the monomer is faster than the dimer by roughly 22 kJ mol-1. Further, the infrared spectrum of sabina ketone was calculated at B3LYP/6-311+G(2d,p); the calculated carbonyl stretching of 1727 cm-1 is in agreement with the experimental range of 1700-1800 cm-1.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
SOZ formation and hydration of the anti-CI of sabinene. (I: intermediate, P: product).
Figure 2
Figure 2
Calculated IR spectra of sabina ketone at B3LYP/6-311+G(2d,p). Epsilon refers to the coefficient of molar absorbance.
Figure 3
Figure 3
Optimized geometries for SOZ formation at B3LYP/6-311G(3df,3pd) for pathway A1.
Figure 4
Figure 4
PES for SOZ formation (pathway A1). Energies calculated at different levels of theory.
Figure 5
Figure 5
Optimized geometries for the reaction of anti-CI with H2O at B3LYP/6-311G(3df,3pd) for pathway B1.
Figure 6
Figure 6
PES for the reaction of anti-CI with H2O (pathway B1). Energies calculated at different levels of theory.
Figure 7
Figure 7
Optimized geometries for the reaction of anti-CI with 2H2O at B3LYP/6-311G(3df,3pd) for pathway B2.
Figure 8
Figure 8
Optimized geometries for the VHP channel via the H2O molecule at B3LYP/6-311G(3df,3pd) for pathway C1.
Figure 9
Figure 9
PES for the VHP channel via the H2O molecule (pathway C1). Energies calculated at different levels of theory.
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References

    1. Lamb B.; Guenther A.; Gay D.; Westberg H. A national inventory of biogenic hydrocarbon emissions. Atmos. Environ. 1987, 21, 1695–1705. 10.1016/0004-6981(87)90108-9. - DOI
    1. Guenther A.; Hewitt C. N.; Erickson D. A global model of natural volatile organic compound emissions. J. Geophys. Res.: Atmos. 1995, 100, 8873–8892. 10.1029/94jd02950. - DOI
    1. Guenther A. B.; Jiang X.; Heald C. L.; Sakulyanontvittaya T.; Duhl T.; Emmons L. K.; Wang X. The model of emissions of gases and aerosols from nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions. Geosci. Model Dev. 2012, 5, 1471–1492. 10.5194/gmd-5-1471-2012. - DOI
    1. Sindelarova K.; Granier C.; Bouarar I.; Guenther A.; Tilmes S.; Stavrakou T.; Müller J.-F.; Kuhn U.; Stefani P.; Knorr W. Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years. Atmos. Chem. Phys. 2014, 14, 9317–9341. 10.5194/acp-14-9317-2014. - DOI
    1. Almatarneh M. H.; Elayan I. A.; Altarawneh M.; Hollett J. W.. Computational Study of the Ozonolysis of Sabinene. Int. J. Environ. Sci.. 2017.