Performance of First-Principles-Based Reaction Class Transition State Theory

Ratkiewicz, Artur; Huynh, Lam K.; Truong, Thanh N.

doi:10.1021/acs.jpcb.5b09564

Cited by 19 publications

(24 citation statements)

References 92 publications

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“…Considering all possible abstraction reaction sites on these alkenes, there are 47 elementary abstraction reactions. These reactions were divided into 10 reaction classes based on the type of carbon atoms in the reaction centers and the RC-TST [13,14]. A full list of all elementary reactions is provided in the Supplementary Materials.…”

Section: Resultsmentioning

confidence: 99%

Reaction Mechanisms and Kinetics of the Hydrogen Abstraction Reactions of C4–C6 Alkenes with Hydroxyl Radical: A Theoretical Exploration

Wang

Sun

Liang

2019

IJMS

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The reaction of alkenes with hydroxyl (OH) radical is of great importance to atmospheric and combustion chemistry. This work used a combined ab initio/transition state theory (TST) method to study the reaction mechanisms and kinetics for hydrogen abstraction reactions by OH radical on C4–C6 alkenes. The elementary abstraction reactions involved were divided into 10 reaction classes depending upon the type of carbon atoms in the reaction center. Geometry optimization was performed by using DFT M06-2X functional with the 6-311+G(d,p) basis set. The energies were computed at the high-level CCSD(T)/CBS level of theory. Linear correlation for the computed reaction barriers and enthalpies between M06-2X/6-311+G(d,p) and CCSD(T)/CBS methods were found. It was shown that the C=C double bond in long alkenes not only affected the related allylic reaction site, but also exhibited a large influence on the reaction sites nearby the allylic site due to steric effects. TST in conjunction with tunneling effects were employed to determine high-pressure limit rate constants of these abstraction reactions and the computed overall rate constants were compared with the available literature data.

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Section: Resultsmentioning

confidence: 99%

Reaction Mechanisms and Kinetics of the Hydrogen Abstraction Reactions of C4–C6 Alkenes with Hydroxyl Radical: A Theoretical Exploration

Wang

Sun

Liang

2019

IJMS

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“…For the calculation of activation energy (eg, reaction CH 3 [88][89][90][91][92][93] have also proposed a GA method for hydrogen abstraction based on supergroups that encompasses the whole reactive moiety by Ghent's group. 94 However, the accuracy of Sabbe's 79 and MF Reyniers's method is influenced by the presence of multiple gauche interactions.…”

Section: Additivity Methods At the Quantum Chemical Levelmentioning

confidence: 99%

“…94 However, the accuracy of Sabbe's 79 and MF Reyniers's method is influenced by the presence of multiple gauche interactions. At the same time, the Supergroup method by Sumathi shows discrepancies between the predictions and the experimentally derived H abstraction from primary and secondary alkanes by methyl radicals [88][89][90][91][92][93] (Table 4). Consequently, reaction models involving resonance corrections and the summation of the electronic and nuclear repulsion energies have been developed to correct those deviations.…”

Section: Additivity Methods At the Quantum Chemical Levelmentioning

confidence: 99%

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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“…Since the specifics of the RC-TST methodology have been detailed in previous reports (Truong, 2000;Ratkiewicz et al, 2016), only the most important features are mentioned here. All processes with the same common structural denominator, also known as reactive moiety, form a class.…”

Section: Reaction Class Transition State Theorymentioning

confidence: 99%

“…The Reaction Class Transition State Theory (RC-TST) provides an accurate theoretical framework. By successful application to numerous reaction classes (Ratkiewicz et al, 2016), including also H abstractions, it has proven to be an effective and time efficient procedure for on-the-fly prediction of the thermal rate constants in a wide temperature range. In this study, an RC-TST framework was employed to derive the kinetic parameters necessary for the estimation of the rate constants of any reaction belonging to the alkane + •OOH → alkyl radical + H 2 O 2 reaction family.…”

Section: Introductionmentioning

confidence: 99%

On-The-Fly Kinetics of the Hydrogen Abstraction by Hydroperoxyl Radical: An Application of the Reaction Class Transition State Theory

Baradyn

Ratkiewicz

2022

Front. Chem.

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A Reaction Class Transition State Theory (RC-TST) is applied to calculate thermal rate constants for hydrogen abstraction by OOH radical from alkanes in the temperature range of 300–2500 K. The rate constants for the reference reaction C2H6 + ∙OOH → ∙C2H5 + H2O2, is obtained with the Canonical Variational Transition State Theory (CVT) augmented with the Small Curvature Tunneling (SCT) correction. The necessary parameters were obtained from M06-2X/aug-cc-pVTZ data for a training set of 24 reactions. Depending on the approximation employed, only the reaction energy or no additional parameters are needed to predict the RC-TST rates for other class representatives. Although each of the reactions can in principle be investigated at higher levels of theory, the approach provides a nearly equally reliable rate constant at a fraction of the cost needed for larger and higher level calculations. The systematic error is smaller than 50% in comparison with high level computations. Satisfactory agreement with literature data, augmented by the lack of necessity of tedious and time consuming transition state calculations, facilitated the seamless application of the proposed methodology to the Automated Reaction Mechanism Generators (ARMGs) programs.

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Performance of First-Principles-Based Reaction Class Transition State Theory

Cited by 19 publications

References 92 publications

Reaction Mechanisms and Kinetics of the Hydrogen Abstraction Reactions of C4–C6 Alkenes with Hydroxyl Radical: A Theoretical Exploration

Reaction Mechanisms and Kinetics of the Hydrogen Abstraction Reactions of C4–C6 Alkenes with Hydroxyl Radical: A Theoretical Exploration

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

On-The-Fly Kinetics of the Hydrogen Abstraction by Hydroperoxyl Radical: An Application of the Reaction Class Transition State Theory

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