Sulfenic acids in the gas phase. Preparation, ionization energies and heats of formation of methane-, ethene-, and benzenesulfenic acid

Tureček, František; Brabec, Libor; Vondrak, T.; Hanuš, V.; Hájíček, Josef; Havlas, Zdeněk

doi:10.1135/cccc19882140

Cited by 24 publications

(23 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In any case, our calculations indicate that this dissociation pathway would not alter the stability of AD due to the high barrier for the elimination process (see Table 1). It is worth mentioning that the global change of the classical potential energy for channel (R1ac) with most of the analyzed high level methods is in the range 2.0/2.8 kcal/mol, in good accordance with the experimental endothermicity at 298 K of 0 ± 3 kcal/mol 25, 26, 90…”

Section: Resultssupporting

confidence: 77%

Electronic structure study of the initiation routes of the dimethyl sulfide oxidation by OH

2005

View full text Add to dashboard Cite

In the present work the potential energy surface (PES) corresponding to the different initiation routes of the oxidation mechanism of DMS by hydroxyl radical in the absence of O(2) has been studied, and connections among the different stationary points have been established. Single-point high level electronic structure calculations at lower level optimized geometries have been shown to be necessary to assure convergence of energy barriers and reaction energies. Our results demonstrate that the oxidation of DMS by OH turns out to be initiated via three channels: a hydrogen abstraction channel that through a saddle point structure finally leads to CH(3)SCH(2) + H(2)O, an addition-elimination channel that firstly leads to an adduct complex (AD) and then via an elimination saddle point structure finally gives CH(3)SOH and CH(3) products, and a third channel that through a concerted pathway leads to CH(3)OH and CH(3)S. The H-abstraction and the addition-elimination channels initiate by a common pathway that goes through the same reactant complex (RC). Our theoretical results agree quite well with the branching ratios experimentally assigned to the formation of the different products. Finally, the calculated equilibrium constants of the formation of the complex AD and the hexadeuterated complex AD from the corresponding reactants, as a function of the temperature, are in good accordance with the experimental values.

show abstract

Section: Resultssupporting

confidence: 77%

Electronic structure study of the initiation routes of the dimethyl sulfide oxidation by OH

2005

View full text Add to dashboard Cite

show abstract

“…This set of 47 molecules excluded 2 potential experimental data sources. Divinyl sulfoxide and methane sulfenic acid each had only a single experimental enthalpy measurement source [33,34] and the measured value for each deviated wildly from our calculated values (8.33 and 10.15 kcal/mol off respectively). This could be due to a weakness of our calculation method or it could be from inaccurate experimental numbers.…”

Section: Benchmarking Of the Calculation Procedurescontrasting

confidence: 59%

Thermochemistry Prediction and Automatic Reaction Mechanism Generation for Oxygenated Sulfur Systems: A Case Study of Dimethyl Sulfide Oxidation

Gillis

Green

2020

ChemSystemsChem

View full text Add to dashboard Cite

Automatic mechanism generation is a powerful approach to understanding complex chemical mechanisms. Here we describe the expansion of an open source mechanism creating software, the Reaction Mechanism Generator or RMG, to oxygenated sulfur systems. This principally involved the expansion of thermochemistry estimation techniques for higher valence oxygenated sulfur molecules. As a demonstration of this new tool, we present an automatically generated mechanism describing the oxidation of dimethyl sulfide. This mechanism is then compared to several experimental studies of dimethyl sulfide oxidation. This case study provides insight into the transformation of sulfur species in the atmosphere, especially the formation pathways of sulfoxides, sulfones, and sulfur dioxide. However, the applications of the newly enhanced mechanism generation tool extend far beyond this single system with obvious use in understanding a variety of atmospheric, petrochemical, and other industrial chemistries.

show abstract

“…Future expansion of this group library will be necessary for modeling more oxidized systems, for which more extensive experimental data are available for benchmarking. [70][71][72][73][74] In addition, regression of BAC and GAV using CCSD(T)-F12 for organic compounds should provide more accurate estimates for thermochemical parameters, and these calculations are currently being conducted. Standard heats of formation, entropies, and heat capacities between 300 and 2400 K were calculated using CBS-QB3 for each of the molecules involved in the reactions investigated in this work, as well as for some additional molecules for use as a training set in GAV regression.…”

Section: Thermochemical Librarymentioning

confidence: 99%

A kinetic and thermochemical database for organic sulfur and oxygen compounds

Class

Aguilera-Iparraguirre

Green

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H2O addition, 8 H2S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in the combustion and desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated using conventional transition state theory, with corrections for internal rotations and tunneling. Additionally, thermochemical parameters were calculated for each of the compounds involved in these reactions. With few exceptions, rate parameters calculated using the two potential energy methods agreed reasonably, with calculated activation energies differing by less than 5 kJ mol(-1). The computed rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling.

show abstract

Sulfenic acids in the gas phase. Preparation, ionization energies and heats of formation of methane-, ethene-, and benzenesulfenic acid

Cited by 24 publications

References 0 publications

Electronic structure study of the initiation routes of the dimethyl sulfide oxidation by OH

Electronic structure study of the initiation routes of the dimethyl sulfide oxidation by OH

Thermochemistry Prediction and Automatic Reaction Mechanism Generation for Oxygenated Sulfur Systems: A Case Study of Dimethyl Sulfide Oxidation

A kinetic and thermochemical database for organic sulfur and oxygen compounds

Contact Info

Product

Resources

About