Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics

A detailed insight of key reactive events related to oxidation and pyrolysis of hydrocarbon fuels further enhances our understanding of combustion chemistry. Though comprehensive kinetic models are available for smaller hydrocarbons (typically C3 or lower), developing and validating reaction mechanisms for larger hydrocarbons is a daunting task, due to the complexity of their reaction networks. The ReaxFF method provides an attractive computational method to obtain reaction kinetics for complex fuel and fuel mixtures, providing an accuracy approaching ab-initio-based methods but with a significantly lower computational expense. The development of the first ReaxFF combustion force field by Chenoweth et al. (CHO-2008 parameter set) in 2008 has opened new avenues for researchers to investigate combustion chemistry from the atomistic level. In this article, we seek to address two issues with the CHO-2008 ReaxFF description. While the CHO-2008 description has achieved significant popularity for studying large hydrocarbon combustion, it fails to accurately describe the chemistry of small hydrocarbon oxidation, especially conversion of CO2 from CO, which is highly relevant to syngas combustion. Additionally, the CHO-2008 description was obtained faster than expected H abstraction by O2 from hydrocarbons, thus underestimating the oxidation initiation temperature. In this study, we seek to systemically improve the CHO-2008 description and validate it for these cases. Additionally, our aim was to retain the accuracy of the 2008 description for larger hydrocarbons and provide similar quality results. Thus, we expanded the ReaxFF CHO-2008 DFT-based training set by including reactions and transition state structures relevant to the syngas and oxidation initiation pathways and retrained the parameters. To validate the quality of our force field, we performed high-temperature NVT-MD simulations to study oxidation and pyrolysis of four different hydrocarbon fuels, namely, syngas, methane, JP-10, and n-butylbenzene. Results obtained from syngas and methane oxidation simulation indicated that our redeveloped parameters (named as the CHO-2016 parameter set) has significantly improved the C1 chemistry predicted by ReaxFF and has solved the low-temperature oxidation initiation problem. Moreover, Arrhenius parameters of JP-10 decomposition and initiation mechanism pathways of n-butylbenzene pyrolysis obtained using the CHO-2016 parameter set are also in good agreement with both experimental and CHO-2008 simulation results. This demonstrated the transferability of the CHO-2016 description for a wide range of hydrocarbon chemistry.