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Molecular conformational effects in H + n -heptane reaction rate calculations

Luo, K; Nasiri, R; (2018) Molecular conformational effects in H + n -heptane reaction rate calculations. Combustion and Flame , 193 pp. 170-176. 10.1016/j.combustflame.2018.03.010. Green open access

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Abstract

Accurate fuel combustion modelling is a matter of immense importance to design clean combustors and reduce greenhouse gas emissions and pollutants. In this Brief Communication, we present the effects of internal dynamics of one n-heptane molecule which are controlling chemical kinetics of hydrogen abstraction reactions through multi-pathway reaction dynamics. It is established that the slope of Arrhenius plots dramatically changes in comparison with the harmonic single static pathway approach in the temperature range of 200–3000 K. We apply a combination of the multiple conformation statistical thermodynamic approach and variational transition-state theory (VTST) to obtain dynamic multi-path rate coefficients (kMP-T-VTST and kMP-LH-VTST). Compared with single-path VTST (kSP-H-VTST) results, the thermal reaction rate coefficients obtained from our MP-VTST calculations differ considerably due to the fact that tunnelling and cross-conformational effects in the reactions, and the anharmonic and quasi-harmonic contributions in multiple conformer molecules cannot be ignored or simplified.

Type: Article
Title: Molecular conformational effects in H + n -heptane reaction rate calculations
Open access status: An open access version is available from UCL Discovery
DOI: 10.1016/j.combustflame.2018.03.010
Publisher version: http://doi.org/10.1016/j.combustflame.2018.03.010
Language: English
Additional information: Copyright © 2018 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY license. (http://creativecommons.org/licenses/by/4.0/)
Keywords: Conformational changes; Multi-pathway reactions; Reaction rate coefficients; Multi-structural statistical thermodynamics theory; Transition state theory
UCL classification: UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Mechanical Engineering
URI: http://discovery.ucl.ac.uk/id/eprint/10046453
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