Theoretical study on the atmospheric reaction of CH<sub>3</sub>O<sub>2</sub>with OH

Bian, He; Zhang, Shiguo; Zhang, Huiming

doi:10.1002/qua.24946

Cited by 12 publications

(39 citation statements)

References 40 publications

(53 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In absence of intersystem crossing (ISC) 3 RC → 1 RC , the reaction CH 3 O 2 +OH ↔ 3 RC will be quasi-equilibrated such that the bimolecular rate constant for the overall triplet channel CH 3 O 2 +OH→ 3 CH 2 O 2 +H 2 O can be found from transition state theory (TST)181920, yielding 3 k bi,3 (298 K)=2.6 × 10 −15 cm 3 molecule −1 s −1 . This channel is therefore entirely negligible, as are the other triplet entrance routes described by Bian et al 16,. all proceeding through transition states that lie even much higher.…”

Section: Resultsmentioning

confidence: 78%

“…They are listed also in Table 2, together with the values for 285 K and 750 hPa, as well as these for 256 K and 400 hPa (see next subsection). Since the other pathways to 1 CH 2 O 2 +H 2 O theoretically characterized by Bian et al 16. and Nguyen et al 17.…”

Section: Resultsmentioning

confidence: 99%

“…TRIOX , with average chemical activation energy < E v > of 31.1 kcal mol −1 (at 298 K) converts rapidly to the product complex 1 PC over the low-lying and very loose TS4, characterized above, far outrunning the other isomerization/decomposition reactions through high-lying transition states16. The rate coefficient integrated over the formation distribution function F ( E th,v ) is evaluated at < k 4 >=2.4 × 10 10 s −1 , implying a TRIOX lifetime of ∼40 ps during which it should lose ∼0.45 kcal mol −1 by collisions at 298 K and 1,013 hPa (see below), shifting down also the energy distribution F ( E th,v ) for 1 PC .…”

Section: Resultsmentioning

confidence: 99%

“…Note that about 45% of the products of activated TRIOX arise via ISC of 1 PC to 3 PC . Of major importance is that TRIOX does not decompose directly but via the complex 1 PC , which enables production of CH 3 OH, while direct methanol formation from CH 3 OOOH would face a quasi-unsurmountable barrier16.…”

Section: Resultsmentioning

confidence: 99%

“…A recent quantum chemical study of CH 3 O 2 +OH by Bian et al 16. could identify only one thermally accessible pathway commensurate with the high measured rate constant: combination of the reactants into an activated methylhydrotrioxide CH 3 OOOH ( TRIOX ), followed by direct dissociation into CH 3 O and HO 2 , which are about 4 kcal mol −1 more stable than the reactant radicals.…”

mentioning

confidence: 95%

See 4 more Smart Citations

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

et al. 2016

View full text Add to dashboard Cite

Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

show abstract

Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 95%

See 3 more Smart Citations

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

et al. 2016

View full text Add to dashboard Cite

show abstract

Theoretical study on the atmospheric reaction of CH₃SH with O₂

Bian

Zhang

et al. 2018

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

A detailed study on the reaction mechanism of CH3SH with O2 was carried out using quantum chemical methods. Eleven singlet pathways and four triplet pathways were found based on CCSD(T)//M06‐2x calculations. The nature of chemical bonding evolution was also studied using electron localization function and atoms in molecules analysis. Moreover, reaction rate constants were calculated between 200 and 800 K at the level of the transition state theory by Wigner tunneling correction. The results suggest that the main products should be CH2SO, H2O, CH3OH, SO, CH4, and SO2, respectively, basically coinciding with the experimental results. The corresponding feasible pathways are channels R7, R8, and R9, respectively, with an effective energy barrier of 56.21 kJ/mol. Obviously, given the low energy barrier similar to the main paths mentioned above, the products CH2SH and HO2 should assume a definite proportion in all possible products, although such species were not yet detected in experiment.

show abstract

A density functional theory study on the atmospheric reaction ofCH₃O₂withHS: Mechanism and kinetics

Zhang

et al. 2020

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The reaction mechanism of CH3O2 and HS was systematically investigated by density functional theory (DFT). Six singlet pathways and seven triplet ones are located on the potential surface (PES). The result indicates that the main products are CH3O and HSO both on the singlet and triplet PES, different from the CH3O2 + OH reaction. Moreover, deformation density (ρdef) and atoms in molecules (AIM) analyses were carried out to further uncover the nature of chemical bonding evolution in the primary pathways. Furthermore, reaction rate constants were calculated in the temperature range from 200 to 1000 K using the transition state theory with the Wigner and Eckart tunneling corrections. Our results can shed light on the title reaction and offer instructions for analogous atmospheric reactions, as well as experimental research in the future.

show abstract

Theoretical study on the atmospheric reaction of CH₃O₂with OH

Cited by 12 publications

References 40 publications

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

Theoretical study on the atmospheric reaction of CH₃SH with O₂

A density functional theory study on the atmospheric reaction ofCH₃O₂withHS: Mechanism and kinetics

Contact Info

Product

Resources

About

Theoretical study on the atmospheric reaction of CH3O2with OH

Cited by 12 publications

References 40 publications

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

Theoretical study on the atmospheric reaction of CH3SH with O2

A density functional theory study on the atmospheric reaction ofCH3O2withHS: Mechanism and kinetics

Contact Info

Product

Resources

About

Theoretical study on the atmospheric reaction of CH₃O₂with OH

Theoretical study on the atmospheric reaction of CH₃SH with O₂

A density functional theory study on the atmospheric reaction ofCH₃O₂withHS: Mechanism and kinetics