Unimolecular decomposition of large organic radicals with low reaction thresholds: Decomposition and reversible isomerization of n‐pentyl radicals

Tsang, Wing; Bedanov, Vladimir M.; Zachariah, Michael R.

doi:10.1002/bbpc.19971010323

Cited by 34 publications

(44 citation statements)

References 14 publications

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“…When these eigenvalues are not well separated, as tends to happen at high temperatures for low barrier processes such as the dissociation of a weakly-bound radical R [37,38], the dissociation and energy relaxation occur in unison and the chemical conversion cannot be represented with a simple rate law.…”

Section: Chemical Reactions and Phenomenological Rate Coefficientsmentioning

confidence: 99%

From theoretical reaction dynamics to chemical modeling of combustion

Klippenstein

2017

Proceedings of the Combustion Institute

232

228

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The chemical modeling of combustion treats the chemical conversion of hundreds of species through thousands of reactions. Recent advances in theoretical methodologies and computational capabilities have transformed theoretical chemical kinetics from a largely empirical to a highly predictive science. As a result, theoretical chemistry is playing an increasingly significant role in the combustion modeling enterprise. The accurate prediction of the temperature and pressure dependence of gas phase reactions requires state-of-the-art implementations of a variety of theoretical methods: ab initio electronic structure theory, transition state theory, classical trajectory simulations, and the master equation. In this work, we illustrate the current state-of-the-art in predicting the kinetics of gas-phase reactions through sample calculations for some prototypical reactions central to combustion chemistry. These studies are used to highlight the success of theory, as well as its remaining challenges, through comparisons with experiments ranging from elementary reaction kinetics studies through to global observations such as flame speed measurements. The illustrations progress from the treatment of relatively simple abstraction and addition reactions, which proceed over a single transition state, through to the complexity of multiwell multichannel reactions that commonly occur in studies of the growth of polycyclic aromatic hydrocarbons. In addition to providing high quality rate prescriptions for combustion modelers, theory will be seen to indicate various shortcomings in the foundations of chemical modeling. Future progress in the fidelity of the chemical modeling of combustion will benefit from more widespread applications of theoretical chemical kinetics and from increasingly intimate couplings of theory, experiment, and modeling.

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Section: Chemical Reactions and Phenomenological Rate Coefficientsmentioning

confidence: 99%

From theoretical reaction dynamics to chemical modeling of combustion

Klippenstein

2017

Proceedings of the Combustion Institute

232

228

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“…The high pressure rate expressions can then be used to project results over all temperatures and pressures. A serious problem is the high temperature situation where rate constants are no longer constant (Tsang, Bedanov & Zachariah, 1996) due to the occurrence of a dynamic situation arising as the molecular energy distributions change. Fortunately at these high temperatures only the branching ratios are of importance.…”

Section: Pah and Sootmentioning

confidence: 99%

Progress in the development of combustion kinetics databases for liquid fuels

Tsang

2004

Data Sci. J.

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This paper describes the present situation regarding chemical kinetic databases for the simulation of the combustion of liquid fuels. Past work in the area is summarized. Much is known about the reactions of the smaller fragments from combustion processes. In order to describe real liquid fuels there is the need for an understanding of how the larger organic fuels are broken down to these fragments. The type of reactions that need to be considered are described and the breakdown of heptane is used as an example.

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“…Our implementation is, however, based on the solution of the timedependent master equation [6] using the Householder and QR algorithms for tridiagonalization and the determination of eigenvalues and functions. This leads to the determination of the complete time evolution, beginning with the initial transient and ending with the steady-state distribution, of the system.…”

Section: Master Equation Treatmentmentioning

confidence: 99%

“…Rate constants have meaning only under the latter conditions. The details of our approach have been summarized in a series of recent papers [6][7][8]. A Windows-based program has been prepared.…”

Section: Master Equation Treatmentmentioning

confidence: 99%