Kinetics of thermoneutral intermolecular hydrogen migration in alkyl radicals

Ratkiewicz, Artur; Bankiewicz, Barbara; Truong, Thanh N.

doi:10.1039/c0cp00293c

Cited by 29 publications

(51 citation statements)

References 30 publications

(48 reference statements)

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“…The uncertainty level of these rates was investigated previously by a direct comparison of the RC-TST rate constants with experimental data. As demonstrated in references [20] and [21], the uncertainty of the RC-TST rate parameters for the reaction classes investigated in this study is comparable to that claimed by the experimentalists, i.e. less than a factor of two (the uncertainty factor defines the range of possible k value of k m / f and k m *f, where k m is the reported value).…”

Section: Computational Detailssupporting

confidence: 56%

“…To successfully apply the RC-TST method to a particular reaction family, the rate constants of the reference reaction for this class is needed. These rates were reported for the reference reactions (being also the simplest ones within a given family) for the 1,3 (1-propyl → 1-propyl), 1,4 (1-butyl → 1-butyl), 1,5 (1-pentyl → 1-pentyl) and 1,6 (1-hexyl → 1-hexyl) intramolecular H-migrations in alkyls [20]. To provide a complete picture of such migrations in alkyl radicals, the 1,7-H shifts should also be taken into account.…”

Section: Introductionmentioning

confidence: 97%

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First-principles kinetics of n-octyl radicals

Ratkiewicz

2013

Progress in Reaction Kinetics and Mechanism

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Kinetics of the isomerisation and unimolecular degradation of n-octyl radicals have been studied with the reaction class transition state theory (RC-TST) method. To explore the kinetics of the 1,7-H migration reactions family, the accurate high-pressure limits of the rate constants for the reference reaction of this class (1-heptyl → 1-heptyl) have been calculated. Finally, both the achievements reported in this paper and previous developments are employed to obtain theoretical branching ratios of intramolecular H-transfers and unimolecular degradations of all possible n-octyl radicals; the results are in satisfactory agreement when compared to experiment. The application of the rates obtained to the simulation of a simple reactor is also reported.

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Section: Computational Detailssupporting

confidence: 56%

Section: Introductionmentioning

confidence: 97%

First-principles kinetics of n-octyl radicals

Ratkiewicz

2013

Progress in Reaction Kinetics and Mechanism

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“…It is well known that tunneling is of great importance for the light particles transfer [28,[39][40][41][42][43][44][45][46][47][48]. As may be seen from Fig.…”

Section: Tunneling Factorsupporting

confidence: 49%

“…Previous applications of RC-TST, hybrid non-local density functional theory (DFT), particularly Becke's half-and-half (BH&H) non-local exchange, and Lee-Yang-Parr (LYP) non-local correlation functional, have been found to be sufficiently accurate for predicting the transition state properties for different classes of reactions [24,[27][28][29]. Recently, there have been a number of new DFT functional developments, such as the non-local M062X functional [33], designed especially for the chemical kinetics purposes.…”

Section: Computational Detailsmentioning

confidence: 99%

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Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

et al. 2013

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This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions at alkane by the ÁC 2 H 5 radical on-the-fly. The linear energy relationship (LER), developed for acyclic alkanes, was also proven to hold for cyclic alkanes. We have derived all RC-TST parameters from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 50 % systematic errors on the average exist in the predicted rate constants using either the RC-TST/LER or RC-TST/BHG method, while in comparison with explicit rate calculations, the differences are within a factor of 2 on the average. The results also show that the RC-TST method is not sensitive to the choice of density functional theory used.

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Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

Shi

2018

Int J Energy Res

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Summary In the modeling of hydrocarbon thermal cracking processes, complicated reaction networks of multicomponent reactants make kinetic parameter predictions very challenging. To solve this problem, the additivity method and Evans‐Polanyi equation were proposed for the prediction of kinetic factors. As the calculation of kinetic parameters using quantum chemical theory was used for higher accuracy, new additivity methods at the quantum theory level were developed for the prediction of thermodynamic kinetic parameters. At the same time, a reaction class transition state theory RC‐TST, analogous to the Evans‐Polanyi equation, was proposed by considering quantum factors for kinetic constant evaluation. Quantum calculation methods promoted mechanistic studies of electronic effects to accurately reveal the kinetic constant rules with different structural factors. Under these circumstances, kinetic parameter predictions by different quantum chemical computation methods were firstly introduced and reviewed. Meanwhile, development of the new additivity method and RC‐TST theory at the quantum chemistry level were summarized, and the new outlook on electronic effects with an appropriate quantum chemical computational method into the new additivity method was conducted to develop more perspicuous and accuracy in a simplified method for the calculation of complicated thermal cracking reaction.

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Kinetics of thermoneutral intermolecular hydrogen migration in alkyl radicals

Cited by 29 publications

References 30 publications

First-principles kinetics of n-octyl radicals

First-principles kinetics of n-octyl radicals

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

Advances in modeling hydrocarbon cracking kinetic predictions by quantum chemical theory: A review

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