Photodissociation of the CH3O and CH3S radical molecules: an ab initio electronic structure study

Bouallagui, Aymen; Zanchet, Alexandre; Yazidi, O.; Jaı̈dane, N.; Bañares, Luis; Senent, María Luisa; Garcı́a-Vela, A.

doi:10.1039/c7cp06054h

Cited by 8 publications

(9 citation statements)

References 64 publications

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“…450 nm. This assignment coincides with the previous MRCI computed energy of 373 nm for the Ã( 2 A 1 ) ← X 2E transition 60 , and it also reasonably explains the aforementioned photochemistry of 2 by the irradiation at 365 nm (Fig. 2c).…”

Section: Resultssupporting

confidence: 91%

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

Shao

Zhu

et al. 2022

Commun Chem

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The atmospheric oxidation of dimethyl sulfide (DMS) yields sulfuric acid and methane sulfonic acid (MSA), which are key precursors to new particles formed via homogeneous nucleation and further cluster growth in air masses. Comprehensive experimental and theoretical studies have suggested that the oxidation of DMS involves the formation of the methylthio radical (CH3S•), followed by its O2-oxidation reaction via the intermediacy of free radicals CH3SOx• (x = 1–4). Therefore, capturing these transient radicals and disclosing their reactivity are of vital importance in understanding the complex mechanism. Here, we report an optimized method for efficient gas-phase generation of CH3S• through flash pyrolysis of S-nitrosothiol CH3SNO, enabling us to study the O2-oxidation of CH3S• by combining matrix-isolation spectroscopy (IR and UV–vis) with quantum chemical computations at the CCSD(T)/aug-cc-pV(X + d)Z (X = D and T) level of theory. As the key intermediate for the initial oxidation of CH3S•, the peroxyl radical CH3SOO• forms by reacting with O2. Upon irradiation at 830 nm, CH3SOO• undergoes isomerization to the sulfonyl radical CH3SO2• in cryogenic matrixes (Ar, Ne, and N2), and the latter can further combine with O2 to yield another peroxyl radical CH3S(O)2OO• upon further irradiation at 440 nm. Subsequent UV-light irradiation (266 nm) causes dissociation of CH3S(O)2OO• to CH3SO2•, CH2O, SO2, and SO3. The IR spectroscopic identification of the two peroxyl radicals CH3SOO• and CH3S(O)2OO• is also supported by 18O- and 13C-isotope labeling experiments.

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Section: Resultssupporting

confidence: 91%

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

Shao

Zhu

et al. 2022

Commun Chem

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“…Specifically, the values of the angles for which calculations have been carried out are y = 101, 201, 301, 401, 501, 601, 701, 751, 801, 851, 901, and the equilibrium angle (i.e., the angle corresponding to the potential-energy minimum) y = 36.771. It is noted that ab initio 2D representations of the potentialenergy surfaces and nonadiabatic couplings have been previously reported for other radicals like CH 3 , 53 and CH 3 O and CH 3 S. 54 In Fig. 5 the calculated PECs are displayed for different values of y.…”

Section: Two-dimensional Representation Of the Vinyl Radicalmentioning

confidence: 56%

An ab initio study of the photodissociation of the vinyl radical

Bouallagui

Zanchet

Bañares

et al. 2022

Phys. Chem. Chem. Phys.

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“…Reactions of them lead to the formation of formaldehyde [38][39][40][41][42]: The high concentration of CO results from the mechanism of an initiation reaction in plasma, i.e., the collision of molecules with high-energy electrons. CH2OH and CH3O radicals are formed from methanol mostly because it has the highest number of bonds with hydrogen (one O-H and three C-H).…”

Section: Plasma Reactormentioning

confidence: 99%

“…Reactions of them lead to the formation of formaldehyde [38][39][40][41][42] Formaldehyde in plasma is rapidly decomposed [43][44][45]:…”

Section: Plasma Reactormentioning

confidence: 99%

Plasma-Catalytic Process of Hydrogen Production from Mixture of Methanol and Water

et al. 2021

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In the present work the process of hydrogen production was conducted in the plasma-catalytic reactor, the substrates were first treated with plasma and then introduced into the catalyst bed. Plasma was produced by a spark discharge. The discharge power ranged from 15 to 46 W. The catalyst was metallic nickel supported on Al2O3. The catalyst was active from a temperature of 400 °C. The substrate flow rate was 1 mol/h of water and 1 mol/h of methanol. The process generated H2, CO, CO2 and CH4. The gas which formed the greatest amount was H2. Its concentration in the gas was ~60%. The conversion of methanol and the production of hydrogen in the plasma-catalytic reactor were higher than in the plasma and catalytic reactors. The synergy effect of the interaction of two environments, i.e., plasma and the catalyst, was observed. The highest hydrogen production was 1.38 mol/h and the highest methanol conversion was 64%. The increased in the discharge power resulted in increasing methanol conversion and hydrogen production.

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Photodissociation of the CH₃O and CH₃S radical molecules: an ab initio electronic structure study

Cited by 8 publications

References 64 publications

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

An ab initio study of the photodissociation of the vinyl radical

Plasma-Catalytic Process of Hydrogen Production from Mixture of Methanol and Water

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