Theoretical studies on energetics and mechanisms of the decomposition of CF3OH

Long, Bo; Tan, Xing-Feng; Ren, Dasen; Zhang, Weijun

doi:10.1016/j.cplett.2010.04.052

Cited by 21 publications

(30 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, our exploratory calculations discussed higher with abstraction agents present in the reaction mixture showed appreciable energy barriers, making these reactions unlikely. Catalytic HF elimination from CF 3 OH, a simpler analogue of CFOCF 2 OH, has been studied intensively theoretically, [23][24][25][26]28,45 and was found to be the key to understanding the rapid loss of CF 3 OH in many experiments, on a time scale of minutes to hours, while other experiments found very long lifetimes. [46][47][48][49][50] The CF 3 OH dissociation was found to be catalyzed by surfaces, by H 2 O and (H 2 O) 2 , as well as by aqueous particles; 23,25,45 our characterization of an H 2 O-catalysed HF-elimination from fluorinated glycolaldehyde with a barrier reduction of B30 kcal mol À1 strongly suggests that CFOCF 2 OH behaves similar to CF 3 OH in this respect.…”

Section: Discussionmentioning

confidence: 99%

“…Finally, the presence of OH and HO 2 radicals can induce additional reductions in barrier height for water or HF complexes of CF 3 OH. [24][25][26] All of these catalysts lower the barrier to formation of HF + CF 2 O by tens of kcal mol À1 ; if sufficient concentrations of catalysts are present, lifetimes of less than a minute 24 are predicted. It appears reasonable to assume that fluorinated glycolaldehyde, CFOCF 2 OH, could undergo similar catalytic conversions, and the appropriate catalysts are known to have been present in the experiments referenced in this work.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Vereecken

Crowley

Amedro

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Product formation in the reaction of perfluorinated methyl vinyl ether, CF 3 OCFQCF 2 , with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable endproducts in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF 3 OCFO, and fluorinated glycolaldehyde, CFOCF 2 OH, both with CF 2 O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF 2 OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Vereecken

Crowley

Amedro

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…In the presence of water vapor, the product channel is reported to shift toward the formation of H 2 SO 4 , which accounts for $ 66% of the products form. Additionally, ab initio methods used by Long et al [9] predict that the HO 2 -H 2 O complex serves to lower the decomposition barrier of CF 3 OH in the atmosphere from 45.7 to $ 0 kcal/mol. The rate constant calculated from this work suggests that the decomposition of CF 3 OH by HO 2 -H 2 O is the main sink for this molecule in the atmosphere.…”

Section: Introductionmentioning

confidence: 98%

Computational study of hexanal peroxy radical–water complexes

Burrell

Clark

Snow

et al. 2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:The results of an ab initio study on a family of hydroxy peroxy radicalwater complexes formed from the oxidation of E-2-hexenal, which constitutes an important component of biogenic atmospheric emissions, are reported. Binding energies for the b-hydroxy-c-peroxy hexanal (b-and c-positions are relative to the carbonyl) radical-water complex and the c-hydroxy-b-peroxy hexanal radical-water complex are predicted to be to 3.8 and 3.6 kcal/mol, respectively, computed at the MP2/6-311þþG(2d,2p)//B3LYP/ 6-311þþG(2d,2p) computational level. Natural bond orbital reveals that conventional hydrogen bonding between the water and the hydroxy and aldehyde functional groups of the radical are primarily responsible for the stability of the complex. It can be shown that the peroxy moiety contributes very little to the stability of the radical-water complexes. Thermochemistry calculations reveal estimated equilibrium constants that are comparable to those recently reported for several hydroxy isoprene radical-water complexes. The results of this report suggest that the hexanal peroxy radical-water complexes are expected to play a significant role in the complex chemistry of the atmosphere.

show abstract

“…HO 2 radical is not only one of the highest concentration oxidants that help in controlling the concentrations of many trace species in the atmosphere but is also of great interest and importance for radical–radical and radical–molecule reactions in the atmosphere . Of great interest is the possible importance of the reactions of HO 2 with FCHO and ClCHO.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Reaction Mechanism and Kinetics of HO₂ with XCHO (X = F, Cl)

Long

Tan

Bao

et al. 2016

Int J of Chemical Kinetics

Self Cite

View full text Add to dashboard Cite

The reactions of HO 2 with FCHO and ClCHO have been theoretically investigated by combining beyond-CCSD(T) electronic structure benchmarks, validated density functional theory, and canonical variational transition state theory with small-curvature tunneling, coupledtorsions anharmonicity, and high-frequency anharmonicity. This investigation explores three different reaction mechanisms: radical addition plus a hydrogen transfer, radical addition, and hydrogen abstraction. The calculated results show that the dominant reaction pathway is the terminal oxygen atom of HO 2 added to the carbon atom of XCHO (X = F, Cl) and simultaneously the hydrogen atom of HO 2 transferred to the oxygen atom of the C=O group in XCHO. The reaction barriers of the other reaction pathways are so high that these processes are negligible in the atmosphere. Although the barrier height of the dominant reaction pathway in the HO 2 + FCHO reaction is 0.61 kcal/mol higher than that of the corresponding HO 2 + ClCHO reaction, the HO 2 + FCHO reaction is faster than the HO 2 + ClCHO reaction because the variational effects of HO 2 + ClCHO is more obvious than that of the HO 2 + FCHO. The present results show that the HO 2 + FCHO reaction may be important in the atmosphere. The present results should be useful in evaluating the atmospheric fate of XCHO (X = F, Cl).

show abstract

Theoretical studies on energetics and mechanisms of the decomposition of CF3OH

Cited by 21 publications

References 26 publications

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Computational study of hexanal peroxy radical–water complexes

Theoretical Study of the Reaction Mechanism and Kinetics of HO₂ with XCHO (X = F, Cl)

Contact Info

Product

Resources

About

Theoretical studies on energetics and mechanisms of the decomposition of CF3OH

Cited by 21 publications

References 26 publications

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCFCF2

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCFCF2

Computational study of hexanal peroxy radical–water complexes

Theoretical Study of the Reaction Mechanism and Kinetics of HO2 with XCHO (X = F, Cl)

Contact Info

Product

Resources

About

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Theoretical Study of the Reaction Mechanism and Kinetics of HO₂ with XCHO (X = F, Cl)