Theoretical study of the OH addition to the β-pinene

Ramírez‐Ramírez, Víctor M.; Peiró-Garcı́a, Julio; Nebot–Gil, Ignacio

doi:10.1016/j.cplett.2004.04.089

Cited by 10 publications

(7 citation statements)

References 20 publications

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“…All TS geometric parameters were similar to the corresponding values for reactants. Similar results for geometric parameters were previously obtained for the theoretical study of OH radical addition to d -limonene, which reported C−O distances in the transition states to be between 2.0 and 2.50 Å. According to that work, four possible prereactive complexes in the reaction pathways were obtained.…”

Section: Resultssupporting

confidence: 87%

“…Vegetation is the most important natural source of these compounds . Biogenic VOCs are assumed to play a dominant role in the chemistry of the lower troposphere and atmospheric boundary layer. − Terpenoids represent the most abundant VOCs emitted by plants, with a global emission rate estimated to be approximately 1150 Tg carbon year −1 . Monoterpenoids in general may have acyclic, monocyclic, and bicyclic structures and occur in nature as hydrocarbons, alcohols, ketones, aldehydes, and ethers.…”

Section: Introductionmentioning

confidence: 99%

“…This compound is also a significant component of indoor cleaner emissions. 6-Methyl-5-hepten-2-one and 6-hydroxy-4-methyl-4-hexenal ( 2 and 3 , respectively) are atmospheric reaction products of biogenically emitted linalool, a terpene emitted from orange blossoms , and from certain pine trees in southern Europe, , as well as trans -geraniol. , Ciccioli et al reported the occurrence of this compound in urban, suburban, and forest areas in a concentration range of 0.1−5 ppbv, with the highest levels close to vegetation. Additionally, diurnal variations of concentration showed midway maxima, and Helmig et al detected it in fall, winter, spring, and summer campaigns in the remote troposphere over Hawaii and in remote areas.…”

Section: Introductionmentioning

confidence: 99%

“…Although several theoretical studies have investigated the addition of OH radicals to other alkenes and terpenes, such as α- and β-pinenes, , only reactions involving ozone with trans -geraniol, 6-hydroxy-4-methyl-4-hexenal, and 6-methyl-5-hepten-2-hexenal have been reported . Two additional sites, which are indicated by the numbers 1 and 2 in 1 , are available in trans -geraniol.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Addition of OH Radicals to trans-Geraniol-(3,7-dimethylocta-2,6-dien-1-ol), 6-Methyl-5-hepten-2-one, and 6-Hydroxy-4-methyl-4-hexenal

et al. 2010

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A combined density functional theory and transition state theory study of the gas-phase addition of OH to 3,7-dimethylocta-2,6-dien-1-ol (trans-geraniol), 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal is presented. In this study, all different possibilities for the addition of the OH radical to the C-C double bonds in trans-geraniol, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal were considered. The geometries, energies, and harmonic vibrational frequencies at each stationary point were determined at the MPW1K/cc-pVDZ and BH&HLYP/cc-pVDZ levels. Global rate coefficients of 0.94 x 10(-10) and 3.1 x 10(-10) cm(3) molecule(-1) s(-1), 2.11 x 10(-11) and 7.53 x 10(-11) cm(3) molecule(-1) s(-1), and 2.70 x 10(-13), and 4.37 x 10(-12) cm(3) molecule(-1) s(-1) were calculated using data obtained at the BH&HLYP/cc-pVDZ and MPW1K/cc-pVDZ levels of theory. These coefficients correspond to the sum of the rate coefficients of the individual paths for trans-geraniol, 6-hydroxy-4-methyl-4-hexenal, and 6-methyl-5-hepten-2-one, when reacting with OH radicals. The calculated rate coefficients are in good agreement with the available experimental data.

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Section: Resultssupporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical Study of the Addition of OH Radicals to trans-Geraniol-(3,7-dimethylocta-2,6-dien-1-ol), 6-Methyl-5-hepten-2-one, and 6-Hydroxy-4-methyl-4-hexenal

et al. 2010

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“…Being produced by more than 300 species, limonene or 4-isopropenyl-1-methyl-cyclohexene, is the most abundant monoterpene. , The reaction of ozone with limonene, which has both endocyclic and exocyclic double bonds, is an important oxidation process in the troposphere. Ozonolysis of limonene is an important source of OH radicals and can also play a significant role in the formation of acid rains and atmospheric aerosols via the oxidation of SO 2 by carbonyl oxides .…”

Section: Introductionmentioning

confidence: 99%

Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Sulfur Dioxide: Ab Initio and DFT Study

Jiang

Ding

2010

J. Phys. Chem. A

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The mechanism of the reaction of the sulfur dioxide (SO(2)) with four stabilized Criegee intermediates (stabCI-CH(3)-OO, stabCI-OO, stabCIx-OO, and stabCH(2)OO) produced via the ozonolysis of limonene have been investigated using ab initio and DFT (density functional theory) methods. It has been shown that the intermediate adduct formed by the initiation of these reactions may be followed by two different reaction pathways such as H migration reaction to form carboxylic acids and rearrangement of oxygen to produce the sulfur trioxide (SO(3)) from the terminal oxygen of the COO group and SO(2). We found that the reaction of stabCI-OO and stabCH(2)OO with SO(2) can occur via both the aforementioned scenarios, whereas that of stabCI-CH(3)-OO and stabCIx-OO with SO(2) is limited to the second pathway only due to the absence of migrating H atoms. It has been shown that at the CCSD(T)/6-31G(d) + CF level of theory the activation energies of six reaction pathways are in the range of 14.18-22.59 kcal mol(-1), with the reaction between stabCIx-OO and SO(2) as the most favorable pathway of 14.18 kcal mol(-1) activation energy and that the reaction of stabCI-OO and stabCH(2)OO with SO(2) occurs mainly via the second reaction path. The thermochemical analysis of the reaction between SO(2) and stabilized Criegee intermediates indicates that the reaction of SO(2) and stabilized Criegee intermediates formed from the exocyclic primary ozonide decomposition is the main pathway of the SO(3) formation. This is likely to explain the large (~100%) difference in the production rate in the favor of the exocyclic compounds observed in recent experiments on the formation of H(2)SO(4) from exocyclic and endocyclic compounds.

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Experimental and theoretical rate coefficients for the gas phase reaction of β-Pinene with OH radical

Dash

Rajakumar

2013

Atmospheric Environment

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Theoretical study of the OH addition to the β-pinene

Cited by 10 publications

References 20 publications

Theoretical Study of the Addition of OH Radicals to trans-Geraniol-(3,7-dimethylocta-2,6-dien-1-ol), 6-Methyl-5-hepten-2-one, and 6-Hydroxy-4-methyl-4-hexenal

Theoretical Study of the Addition of OH Radicals to trans-Geraniol-(3,7-dimethylocta-2,6-dien-1-ol), 6-Methyl-5-hepten-2-one, and 6-Hydroxy-4-methyl-4-hexenal

Reaction of Stabilized Criegee Intermediates from Ozonolysis of Limonene with Sulfur Dioxide: Ab Initio and DFT Study

Experimental and theoretical rate coefficients for the gas phase reaction of β-Pinene with OH radical

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