Validation of a Database of Formation Enthalpies and of Mid-Level Model Chemistries

Simmie, John M.; Sheahan, Jerome

doi:10.1021/acs.jpca.6b07503

Cited by 28 publications

(23 citation statements)

References 67 publications

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“…Besides CBS‐QB3, also the G4 composite approach has been widely used for calculations of energetic profiles of chemical processes . Most recently, Simmie and Sheahan reported that among the composite methods CBS‐QB3, CBS‐APNO, G3, and G4, the G4 approach is the most accurate one for calculating enthalpies of formation via the atomization procedure . Therefore, the PES obtained by Carstensen and Dean was reevaluated at the G4 level of theory.…”

Section: Resultsmentioning

confidence: 99%

A Shock Tube and Modeling Study about Anisole Pyrolysis Using Time-Resolved CO Absorption Measurements

Shu

Herzler

Peukert

et al. 2017

Int. J. Chem. Kinet.

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The pyrolysis of anisole (C 6 H 5 OCH 3 ) was studied behind reflected shock waves via highly sensitive absorption measurements of CO concentration using a rotational transition in the fundamental vibrational band near 4.7 µm. Time-resolved CO mole fractions were monitored in shock-heated C 6 H 5 OCH 3 /Ar mixtures between 1000 and 1270 K at 1.3-1.6 bar. The decomposition of C 6 H 5 OCH 3 proceeds exclusively via homolytic dissociation, with reaction rate k 1 , forming methyl (CH 3 ) and phenoxy (C 6 H 5 O) radicals. The subsequent decomposition of C 6 H 5 O by ring rearrangement and bond dissociation yields CO. To determine the rate constant k 2 of C 6 H 5 O decomposition avoiding secondary reactions, allyl phenyl ether (C 6 H 5 OC 3 H 5 ) was used as an alternative source for C 6 H 5 O. Its decomposition was studied between 970 and 1170 K at ß1.4 bar. The potential-energy surface of C 6 H 5 O dissociation has been reevaluated at the G4 level of theory. Rate constants determined from unimolecular rate theory are in good agreement with the present experiments. However, the obtained rates k 2 = 9.1 × 10 13 exp(−220.3 kJ mol −1 /RT)s −1 are significantly higher than those reported before (factor 6, 2, and 1.5 faster than those data reported by Lin and Lin, J. Phys. Chem. 1986, 90, 425-431;Frank et al., 1994; Carstensen and Dean, 2012, respectively). Good agreement was found between the measured CO concentration profiles and simulations based on the mechanism of Nowakowska et al. after substituting k 2 by the value obtained from experiments on C 6 H 5 OC 3 H 5 in this work. The

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Section: Resultsmentioning

confidence: 99%

A Shock Tube and Modeling Study about Anisole Pyrolysis Using Time-Resolved CO Absorption Measurements

Shu

Herzler

Peukert

et al. 2017

Int. J. Chem. Kinet.

View full text Add to dashboard Cite

show abstract

“…The G4 composite approach has been widely used for calculations of potential energy surfaces (PES) of chemical processes. Most recently, Simmie and Sheahan reported that among the composite methods (CBS‐QB3, CBS‐APNO, G3, G4), the G4 approach is the most accurate one for calculating enthalpies of formation via the atomization procedure for chemical species made up of C, H, N, and O. We assume that this conclusion on the G4 method applies on systems containing silicon.…”

Section: Methodsmentioning

confidence: 96%

Response surface and group additivity methodology for estimation of thermodynamic properties of organosilanes

Janbazi

Hasemann

Schulz

et al. 2018

Int J of Chemical Kinetics

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Group additivity methods simplify the determination of thermodynamic properties of a wide range of chemically related species involved in detailed reaction schemes. In this paper, we expand Benson's group additivity method to organosilanes. Based on quantum‐chemical calculations, the thermodynamic data of 22 stable silicon‐organic species are calculated, presented in the form of NASA polynomials, and compared to the available experimental data. Based on this theoretical database, a complete set of 24 Si‐ and C‐atom‐centered, single‐bonded and nonradical group additivity values for enthalpy of formation, standard entropy, and heat capacity at temperatures from 200 to 4000 K is derived through unweighted multivariate linear regression.

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“…There have been a number of updates and additions to the group additivity values since the original groups were derived , and work in this area is continuing. There are also several, valuable calculation sets and critical evaluation reviews on thermochemical properties that provide extensive listings of reference values for aliphatic, oxygenated, sulfur‐ and nitrogen‐bearing organic compounds and radicals .…”

Section: Sars For Thermochemistrymentioning

confidence: 99%

Perspective on Mechanism Development and Structure‐Activity Relationships for Gas‐Phase Atmospheric Chemistry

Vereecken

Aumont

Barnes

et al. 2018

Int J of Chemical Kinetics

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This perspective gives our views on general aspects and future directions of gasphase atmospheric chemical kinetic mechanism development, emphasizing on the work needed for the sustainable development of chemically detailed mechanisms that reflect current kinetic, mechanistic, and theoretical knowledge. Current and future mechanism development efforts and research needs are discussed, including software-aided autogeneration and maintenance of kinetic models as a future-proof approach for atmospheric model development. There is an overarching need for the evaluation and extension of structure-activity relationships (SARs) that predict the properties and reactions of the many multifunctionalized compounds in the atmosphere that are at the core of detailed mechanisms, but for which no direct chemical data are available. Here, we discuss the experimental and theoretical data needed to support the development of mechanisms and SARs, the types of SARs relevant to atmospheric chemistry, the current status and limitations of SARs for various types of atmospheric reactions, the status of thermochemical estimates needed for mechanism development, and our outlook for the future. The authors have recently formed a SAR evaluation working group to address these issues. C

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Validation of a Database of Formation Enthalpies and of Mid-Level Model Chemistries

Cited by 28 publications

References 67 publications

A Shock Tube and Modeling Study about Anisole Pyrolysis Using Time-Resolved CO Absorption Measurements

A Shock Tube and Modeling Study about Anisole Pyrolysis Using Time-Resolved CO Absorption Measurements

Response surface and group additivity methodology for estimation of thermodynamic properties of organosilanes

Perspective on Mechanism Development and Structure‐Activity Relationships for Gas‐Phase Atmospheric Chemistry

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