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

Bian, He; Xu, Bin; Zhang, Honghong; Wang, Qian; Zhang, Huiming; Zhang, Shiguo; Xia, Daohong

doi:10.1002/qua.25822

Cited by 6 publications

(6 citation statements)

References 82 publications

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“…Interestingly, the energy barrier for reverse reaction path is high up to 188.97 kJ/mol. It indicates that the reverse reaction are difficult to occur, which is well consistent with our previous study …”

Section: Resultssupporting

confidence: 93%

“…Vibration frequency in 1 TS6 displays the mode of H1 shift from C to O1, similar to 1 TS5. 1 TS7 display the just opposite hydrogen transfer, that is, H4 shift from O2 to C leading to the formation of P6 (CH 3 SH + 1 O 2 ) . The barrier is 180.65 kJ/mol by calculation, which is higher than that of 1 TS6.…”

Section: Resultsmentioning

confidence: 88%

“…Moreover, 6 intermediates, 14 TSs and 9 kinds of products may exist. In addition, some related atmospheric reactions were helpful for understanding the nature of the title reaction more deeply …”

Section: Resultsmentioning

confidence: 99%

“…The above investigations indicate that the main products for the reaction of CH 3 S with HO 2 may be 1 CH 2 S, H 2 O 2 , 3 O 2 , and CH 3 SH. In the latest study on the mechanism of CH 3 SH + O 2 , we found a possible pathway, that is, CH 3 SH + 3 O 2 → CH 2 SH + HO 2 . Interestingly, the energy barrier of its reverse reaction (CH 2 SH + HO 2 → CH 3 SH + 3 O 2 ) is only 12.94 kJ/mol.…”

Section: Introductionmentioning

confidence: 95%

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Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study

Bian

Zhang

Pei

et al. 2019

Int J of Quantum Chemistry

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Density functional theory was adopted in this work to reveal the reaction mechanism of CH2SH with HO2. Reaction rate constants were computed from 200 to 2000 K using the transition state theory combined with Wigner and Eckart tunneling correction. Moreover, localized orbital locator, atoms in molecules and Mayer bond order analyses were used to study the essence of chemical bonding evolution. Eleven singlet paths and three triplet ones are located on the potential surface (PES). The results show that the main products on the singlet PES are 1CH2S and H2O2, whereas on the triplet PES they are CH3SH + 3O2, which are coincident with the similar reaction of CH3S and HO2. This conclusion is also supported by rate constant calculation results. Interestingly, all the possible paths are involved in the hydrogen transfer. The results have provided underlying insights to the analogous reactions and further experimental studies.

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Section: Resultssupporting

confidence: 93%

Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

See 2 more Smart Citations

Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study

Bian

Zhang

Pei

et al. 2019

Int J of Quantum Chemistry

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“…[17,18] Alternatively, theoretical calculations can be helpful in identifying the main reaction pathway and clarifying the reaction mechanism. [19][20][21] Yang et al [22] investigated the cycloaddition reaction of O 3 to AA using density functional theory for the first time, whereas they did not perform further research on the subsequent reactions of primary ozonide (POZ). Recently, Elakiya et al [23] further studied the atmospheric ozonolysis mechanism and kinetics of AA using quantum chemical and kinetic calculations.…”

mentioning

confidence: 99%

Theoretical reinvestigation of the ozonolysis mechanism of allyl alcohol

Lei

Wang

2020

Int J of Quantum Chemistry

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Allyl alcohol (AA) is the simplest unsaturated alcohol. Ozonolysis is one of the key removal processes for AA in the atmosphere. However, a recent theoretical study suggests that the ozonolysis of AA cannot feasibly occur in atmospheric conditions because of the high barrier (96 kcal/mol) involved in the primary ozonide (POZ) decomposition. In this work, the ozonolysis mechanism of AA was reinvestigated theoretically. The computed barrier for POZ decomposition is only 20 kcal/mol. Therefore, the AA ozonolysis can take place in the atmosphere, consistent with the experimental conclusions. Moreover, two new Criegee intermediates (syn-and anti-AA-CI) were found to be produced in this reaction. The wave function analyses indicate that there exists an intermolecular hydrogen bond in syn-AA-CI, which significantly affects its unimolecular decomposition and reactions with H 2 O. Compared with the normal reactions of anti-CI-AA, the stabilized syn-AA-CI has two distinct isomerization channels: (i) addition of OH group to the reactive sites of CI forming an ethylene oxide (HOOCH 2 OCH 2) and (ii) double H-transfer producing HOOCH 2 CHO. Meanwhile, the addition of H 2 O in syn-AA-CI also exhibits two different pathways. One is the unique addition-coupled double H-transfer, and the other is the additioncoupled single H-transfer, both leading to the formation of CH 2 (OH)CH(OH)OOH.

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Interstitial Atomic Bi Charge‐Alternating Processor Boosts Twofold Molecular Oxygen Activation Enabling Rapid Catalytic Oxidation Reactions at Room Temperature

Lian

et al. 2022

Adv Funct Materials

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Molecular O2 activation on metallic oxide‐based catalysts surfaces is pivotal for catalytic oxidation reactions but highly depends on the O2 activation pathways or mechanisms. Thus, comprehensively understanding the mechanism of efficient O2 activation is conducive to extending the fundamental principles for O2 activation theories and designing novel catalysts for catalytic oxidation reactions. In this study, it is declared that the interstitial atomic Bi (IA Bi) anchored in the lattice interstice of MnO2 (Bi/MnO2) is capable of triggering an alternative twofold O2 activation boosting the catalytic oxidation reactions at room temperature. Explicitly, the IA Bi facilely induces the local lattice distortion reconstructing the local charge landscape, thus weakening the O2 dissociation energy barrier by elongating the OO bond length. And, the charge‐alternating process engineered by the IA Bi drives the alternative twofold O2 activation of the adjacent lattice oxygen and adsorbs dangling oxygen assisted by the consecutive O2 replenishment. Conclusively, this study not only declares the role of IA Bi in driving the charge‐alternating process during the twofold O2 activation but also extends the fundamental principles toward O2 activation mechanisms for catalytic oxidation reactions via atomic makeup engineering.

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Theoretical study on the atmospheric reaction of CH₃SH with O₂

Cited by 6 publications

References 82 publications

Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study

Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study

Theoretical reinvestigation of the ozonolysis mechanism of allyl alcohol

Interstitial Atomic Bi Charge‐Alternating Processor Boosts Twofold Molecular Oxygen Activation Enabling Rapid Catalytic Oxidation Reactions at Room Temperature

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Theoretical study on the atmospheric reaction of CH3SH with O2

Cited by 6 publications

References 82 publications

Insight into the reaction mechanism of CH2SH with HO2: A density functional theory study

Insight into the reaction mechanism of CH2SH with HO2: A density functional theory study

Theoretical reinvestigation of the ozonolysis mechanism of allyl alcohol

Interstitial Atomic Bi Charge‐Alternating Processor Boosts Twofold Molecular Oxygen Activation Enabling Rapid Catalytic Oxidation Reactions at Room Temperature

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Theoretical study on the atmospheric reaction of CH₃SH with O₂

Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study

Insight into the reaction mechanism of CH₂SH with HO₂: A density functional theory study