Infrared spectrum and ab initio calculations of matrix isolated methanesulfonic acid species and its 1:1 water complex

Givan, A.; Loewenschuss, A.; Nielsen, Claus J.

doi:10.1016/j.molstruc.2005.03.015

Cited by 43 publications

(54 citation statements)

References 53 publications

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“…952 values available in the literature for MSA. 22,23 The present values are in very good agreement with the experimental results, with a average error of 2%. For MSIA, there are not experimental results in the literature.…”

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confidence: 89%

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

Carvalho¹,

Silva²,

Resende³

2011

J. Braz. Chem. Soc.

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As propriedades estruturais, espectroscópicas e termodinâmicas de duas espécies de enxofre de interesse atmosférico, ácidos metanosulfínico (CH 3 S(O)OH, MSIA) e metanosulfônico (CH 3 S(O) 2 OH, MSA) foram determinadas no nível de CCSD(T)/CBS (coupled-cluster with single and double and perturbative triple excitations/complete basis set) de teoria. Duas conformações foram encontradas para o ácido metanosulfínico e o valor médio determinado para a entalpia de formação foi -337,2 kJ mol -1 . Para o ácido metanosulfônico, o resultado para a entalpia de formação foi 566,2 kJ mol -1 . Escolhendo cuidadosamente as reações químicas e considerando a existência de duas conformações de MSIA, esta investigação reporta os valores mais precisos de DH f disponíveis até agora para estas espécies.The structural, spectroscopic and thermochemical properties of two sulfur species of atmospheric interest, methanesulfinic (CH 3 S(O)OH, MSIA) and methanesulfonic (CH 3 S(O) 2 OH, MSA) acids, were determined at the CCSD(T)/CBS (coupled-cluster with single and double and perturbative triple excitations/complete basis set) level of theory. Two stable conformers were found to the methanesulfinic acid, and the determined average value for the enthalpy of formation (DH f ) was -337.2 kJ mol -1 . For methanesulfonic acid, the determined enthalpy of formation was 566.2 kJ mol -1 . By carefully choosing of the chemical reactions and considering the existence of two MSIA conformers, this investigation reports the most accurate DH f values available to date for these species. Keywords: dimethyl sulfide, enthalpy of formation, CCSD(T)/CBS theory IntroductionDimethyl sulfide (DMS), generated in the ocean by phytoplankton, is an important natural source of sulfur in the atmosphere. 1 The main final products of its atmospheric decomposition are sulfuric acid and sulfate ions, which are key species in the climate regulation, due to the fact that they are precursors of aerosols. Sulfur aerosols act in the global warming producing a negative radiative forcing, dispersing the solar radiation and increasing the albedo. 2 Besides, due to the low gas pressure and polarity, these species can act as cloud condensation nuclei (CCN), condensing water molecules. 3,4 Several experimental and theoretical investigations of the oxidation of DMS in gas phase were conducted 5-7 and studies for OH-initiated reaction had revealed methanesulfonic acid (CH 3 S(O) 2 OH, MSA) 8 and methanesulfinic acid (CH 3 S(O) OH, MSIA) 9 as two key intermediates. In general, there are some difficulties in the characterization of the products, and the values of product yields reported can differ significantly. It is generally accepted that MSA is produced from the OH addition to DMS, in a mechanism highly dependent on temperature and O 2 partial pressure. On the other hand, the presence of MSIA in the atmospheric decomposition of DMS was proposed by Yin et al., 10 as a second-generation product of the DMS oxidation. However, the mechanism and the yields of MSIA formation were reasons of ...

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supporting

confidence: 89%

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

Carvalho¹,

Silva²,

Resende³

2011

J. Braz. Chem. Soc.

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“…Despite of the fact that both acids are very strong [27,28], the energy to transfer an H + ion from the solution phase to the electrode surface to form an adsorbed hydrogen atom must be higher in the presence of more structured water. This seems to be the case in the [29,30]. None of these bands or others related to MSA decomposition were observed in the SNIFTIR spectra.…”

mentioning

confidence: 72%

Interaction of water with methanesulfonic acid on Pt single crystal electrodes

Sandoval

Suárez-Herrera

Climent

et al. 2015

Electrochemistry Communications

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The electrochemical behavior of methanesulfonic acid on platinum single crystal electrode surfaces is investigated by cyclic voltammetry and infrared spectroscopy measurements.The results are compared with those characteristic of perchloric and trifluoromethanesulfonic acids. The differences on the voltammetric profile are interpreted in terms of the effect of the anion on the structure of water. No adsorbed species are detected by infrared spectroscopy.

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“…The peak at 1126 cm -1 and the shoulder around 1174 cm -1 are assigned to the bending mode of undissociated S-O-H and the SO 2 symmetric stretch respectively, as suggested by previous studies. 22,58 Molecular MSA can easily form hydrogen bonds with water and itself. 22 In pure MSA, self-association to form cyclic dimers should prevail, while a 1:1 MSA-water complex exists in a 0.5 x MSA solution.…”

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confidence: 99%

Interfacial Molecular Organization at Aqueous Solution Surfaces of Atmospherically Relevant Dimethyl Sulfoxide and Methanesulfonic Acid Using Sum Frequency Spectroscopy and Molecular Dynamics Simulation

et al. 2010

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The molecular organization at the aqueous dimethyl sulfoxide (DMSO) and methanesulfonic acid (MSA) surfaces was investigated using vibrational sum frequency generation (VSFG) spectroscopy and molecular dynamics (MD) simulation. The molecular orientation of surface DMSO and MSA is deduced based on the VSFG spectra of both C-H stretch and S-O stretch regions. The S-O stretch region was studied for the first time and is shown to be critical in molecular orientation determination. On average, the CH(3) groups of DMSO and MSA are preferentially pointing outward into the air. However, the DMSO S═O group points slightly inward away from the surface, while the SO(3) vector of dissociated MSA points nearly straight down. In addition, MD simulations reveal that the orientation distribution of surface DMSO is relatively broad in contrast with a narrow distribution of surface MSA, which agrees with the experiment findings.

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Infrared spectrum and ab initio calculations of matrix isolated methanesulfonic acid species and its 1:1 water complex

Cited by 43 publications

References 53 publications

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

Theoretical determination of the properties of Methanesulfinic and Methanesulfonic acids

Interaction of water with methanesulfonic acid on Pt single crystal electrodes

Interfacial Molecular Organization at Aqueous Solution Surfaces of Atmospherically Relevant Dimethyl Sulfoxide and Methanesulfonic Acid Using Sum Frequency Spectroscopy and Molecular Dynamics Simulation

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