title: Molecular dynamics simulation of the low-temperature partial oxidation of CH4.
abstract: Low-temperature partial oxidation of methane was investigated using reactive molecular dynamics (MD) and quantum mechanical (QM) methods. In particular, the ReaxFF hydrocarbon force field [Chenoweth, K.; et al. J. Phys. Chem. A 2008, 112, 1040] was employed to simulate a [20 CH(4) + 10 O(2)] model system at 500 degrees C. The chemical mechanism of the partial oxidation of methane was proposed on the basis of analysis of the computed trajectory of this model system. The partial oxidation of methane was observed to be initiated by the abstraction of hydrogen from CH(4) by O(2) and the atomization of CH(4) itself. Subsequent radical recombination between hydrogen atoms and the dehydrogenation of CH(4) were the primary pathways by which H(2) was formed. In agreement with current models of low-temperature combustion, radicals including H(3)C-OO and H(2)C-OO were also observed during the MD simulation. The observed reaction mechanism was subsequently analyzed using QM methods. For instance, structural features of prominent radical species observed during the MD simulation were analyzed using density functional theory (DFT) and coupled-cluster (CCSD(T)) methods. Enthalpies of reaction of all observed chemical processes were calculated using DFT and the W1 composite method. Where possible, comparisons with experimental data were made.
authors.affiliation: Priority Research Centre for Energy, Discipline of Chemical Engineering, Faculty of Engineering and Built Environment, The University of Newcastle, University Drive, Callaghan, NSW 2308, Australia. alister.page@newcastle.edu.au
authors.forename: Alister J
authors.initials: AJ
authors.lastname: Page
authors.forename: Behdad
authors.initials: B
authors.lastname: Moghtaderi
mesh_terms: D005609:Free Radicals / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D008697:Methane / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics
chemical_list: D005609:Free Radicals; D006859:Hydrogen; D008697:Methane; D010100:Oxygen