A reactive molecular dynamics study of the effects of an electric field on n-dodecane combustion

EM Kritikos and A Lele and ACT van Duin and A Giusti, COMBUSTION AND FLAME, 244, 112238 (2022).

DOI: 10.1016/j.combustflame.2022.112238

A reactive Molecular Dynamics (MD) study of n-dodecane combustion at high temperatures under externally applied electrostatic fields is performed to investigate their effect on chemical kinetics. A local charge equilibration method is used to enable charge transfers up to the overlap of the atomic orbitals and introduce molecular polarization induced by an electric field. The atomic charges of an isolated ndodecane molecule with and without external electrostatic fields are first compared with Density Functional Theory (DFT) computations, to assess the accuracy of the charge equilibration method and its ability to capture polarization. Then, the impact of external electrostatic fields on the reaction kinetics of fuel, oxidizer and products is studied for a range of ambient temperatures and densities. The activation energy and pre-exponential factor of Arrhenius-type reactions under various electrostatic fields are also investigated by performing Nudged Elastic Band (NEB) computations on selected reactions' Minimum Energy Path (MEP) and by analysing the collision frequency, respectively. Results show that the atomic charge transfers due to close interactions and molecular polarisation are relatively weak in all investigated conditions, leading to the necessity of strong external electric fields to induce changes to chemical kinetics. The consumption rate of n-dodecane decreases for strong electrostatic fields, whereas for low values of the electrostatic field strength no clear trend is observed. In addition, at high temperature and density conditions, oxygen consumption increases under strong electrostatic fields, whereas the opposite trend is observed as the temperature and density decrease. NEB analysis shows alterations of the activation energy up to 2.3 kcal/mol for oxygen compound reactions with varying strength of the external electrostatic field. Furthermore, analysis of the translational, rotational and vibrational kinetic energy modes and collision frequency reveals the influence of translational motion and molecular stabilization on the reaction rates. The kinetics of oxygen molecules was found to be of primary importance to determine the reaction behaviour under external electrostatic fields, as oxygen molecules have a direct effect on the oxidation reactions and also indirectly affect n-dodecane pyrolysis when an electrostatic field is present. This study provides fundamental understanding of the interactions between heavy hydrocarbons and electrostatic fields for the development of future hybrid thermal-electrical technologies.(c) 2022 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/ )

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