Structure and photochemistry of nitrous acid–methanethiol complexes in solid argon

Grzechnik, Katarzyna; Mielke, Zofia

doi:10.1016/j.molstruc.2012.03.043

Cited by 4 publications

(13 citation statements)

References 47 publications

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“…1092, 1064 cm −1 (see Figure 7A,C) that occur in the region of the ν(SH) and γ(CH 3 ) vibrations of CH 3 SH. 25,55 In the spectra of the DMDS/HO 15 NO/Ar matrixes the most characteristic absorption is shifted to the 1710−1660 cm −1 region and the three subpeaks appear at 1689.0, 1683.5, and 1676.0 cm −1 , respectively. The 2550, 1092, and 1064 cm −1 bands are not sensitive to isotopic substitution.…”

Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

“…It has to be remembered that ammonia is also present in the matrixes as contamination; however, being trapped in a different matrix cage from the DMDS···HONO complex, it does not participate in the matrix photochemistry as demonstrated in our earlier studies on CO/ HONO/Ar, 24 CH 2 NOH/HONO/Ar, 56 and CH 3 SH/HONO/ Ar systems. 25 The DFT/B3LYP/aug-cc-pVTZ calculations revealed that the CH 3 SONO molecule can adopt two stable structures, namely cis and trans isomers ( Figure S8, Supporting Information). Geometric parameters of both isomers are Spectra a and c were recorded after matrix deposition, and spectra b, d, e, and f were recorded after matrix exposure to λ > 345 nm radiation for 240 min.…”

Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

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OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

et al. 2013

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We report the results of the theoretical study of (•)OH-induced oxidative cleavage of dimethyl disulfide (DMDS) and the experimental study of the CH3SSCH3 + (•)OH reaction in the presence of (•)NO. Infrared low temperature argon matrix studies combined with ab initio calculations allowed us to identify cis-CH3SONO, which evidences the formation of the CH3SO(•) and CH3SH molecules in the course of the CH3SSCH3 + (•)OH reaction. Ab initio/quantum chemical topology calculations revealed details of the oxidative cleavage of dimethyl disulfide, which is a complex multistep process involving an alteration of S-O and S-S covalent bonds as well as a hydrogen atom transfer. The ability of delocalization of the unpaired electron density by sulfur atoms and a formation of a hydrogen bond by CH3SO(•) and CH3SH are the factors which seem to explain antiradical properties of DMDS.

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Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

et al. 2013

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“…After the irradiation process was completed the samples were annealed to 30 K for 10 min and then cooled again to 11 K, and the spectra of the annealed matrices were recorded. Ammonia was present in the studied matrices as a contamination, but it did not participate in the photochemical processes similarly like in our earlier studied systems. , All spectra (resolution 0.5 cm –1 ) were registered at 11 K in a reflection mode with Bruker 113v FTIR spectrometer using liquid N 2 -cooled MCT detector.…”

Section: Methodsmentioning

confidence: 93%

“…The HONO/Ar mixtures were prepared in the same way as previously described. 28 HONO (and NH 3 ) was evaporated from small glass tube containing NH 4 NO 2 maintained at ca. 15 °C placed in the vacuum vessel of the cryostat ca.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Ammonia was present in the studied matrices as a contamination, but it did not participate in the photochemical processes similarly like in our earlier studied systems. 28,36 All spectra (resolution 0.5 cm −1 ) were registered at 11 K in a reflection mode with Bruker 113v FTIR spectrometer using liquid N 2 -cooled MCT detector.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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The OH-Initiated Oxidation of CS₂in the Presence of NO: FTIR Matrix-Isolation and Theoretical Studies

et al. 2016

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We studied the photochemistry of the carbon disulfide-nitrous acid system with the help of Fourier transform infrared (FTIR) matrix isolation spectroscopy and theoretical methods. The irradiation of the CS2···HONO complexes, isolated in solid argon, with the filtered output of the mercury lamp (λ > 345 nm) was found to produce OCS, SO2, and HNCS; HSCN was also tentatively identified. The (13)C, (15)N, and (2)H isotopic shifts as well as literature data were used for product identifications. The evolution of the measured FTIR spectra with irradiation time and the changes in the spectra after matrix annealing indicated that the identified molecules are the products of different reaction channels: OCS being a product of another reaction path than SO2 and HNCS or HSCN. The possible reaction channels between SC(OH)S/SCS(OH) radicals and NO were studied using DFT/B3LYP/aug-cc-pVTZ method. The SC(OH)S and/or SCS(OH) intermediates are formed when HONO attached to CS2 photodissociates into OH and NO. The calculations indicated that SC(OH)S radical can form with NO two stable adducts. The more stable SC(OH)S···NO structure is a reactant for a simple one-step process leading to OCS and HONS molecules. An alternative, less-stable complex formed between SC(OH)S and NO leads to formation of OCS and HSNO. The calculations predict only one stable complex between SCS(OH) radical and NO, which can dissociate along two channels leading to HNCS and SO2 or HSCN and SO2 as the end products. The identified photoproducts indicate that both SC(OH)S and SCS(OH) adducts are intermediates in the CS2 + OH + NO reaction leading to different reaction products.

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A hydrogen-bonded CH2F2⋯CO complex: ab initio and matrix isolation study

Sosulin

Tyurin

Feldman

2020

Journal of Molecular Structure

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Structure and photochemistry of nitrous acid–methanethiol complexes in solid argon

Cited by 4 publications

References 47 publications

OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

The OH-Initiated Oxidation of CS₂in the Presence of NO: FTIR Matrix-Isolation and Theoretical Studies

A hydrogen-bonded CH2F2⋯CO complex: ab initio and matrix isolation study

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Structure and photochemistry of nitrous acid–methanethiol complexes in solid argon

Cited by 4 publications

References 47 publications

OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

OH-Induced Oxidative Cleavage of Dimethyl Disulfide in the Presence of NO

The OH-Initiated Oxidation of CS2in the Presence of NO: FTIR Matrix-Isolation and Theoretical Studies

A hydrogen-bonded CH2F2⋯CO complex: ab initio and matrix isolation study

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The OH-Initiated Oxidation of CS₂in the Presence of NO: FTIR Matrix-Isolation and Theoretical Studies