A theoretical kinetic study of ĊH3 + ṄH2: From electronic structure to NH3/CH4 combustion modelling implications

Zhu, Yuxiang, Klippenstein, Stephen J., Curran, Henry J., & Zhou, Chong-Wen. (2025). A theoretical kinetic study of ĊH3 + ṄH2: From electronic structure to NH3/CH4 combustion modelling implications. Combustion and Flame, 277, 114232. https://doi.org/10.1016/j.combustflame.2025.114232

Abstract

Carbon–nitrogen interaction reactions play an important role in governing the reactivity of ammonia blended fuels. However, there remains uncertainties regarding their detailed reaction pathways and rate constants, hampering the development of high-fidelity chemical kinetic models. In this study, the kinetics of ĊH3 + ṄH2, a key C–N interaction reaction in ammonia/methane blend combustion have been investigated. The potential energy surface has been explored using the high-level ANL0F method, yielding highly accurate stationary point energies that agree with ATcT values within 0.1 kcal mol–1. Variable reaction coordinate transition state theory is used to treat the barrierless association and decomposition reaction channels, based on directly sampled radical-radical interaction energies at the CASPT2-F12(2e,2o)/cc-pVTZ-F12 level of theory. The minimum transitional mode numbers of states obtained are then coupled with the RRKM/master equation to calculate temperature- and pressure-dependent rate constants. Our a priori calculations capture available experimental measurements from the literature very well. The calculated rate constants have been incorporated into an NH3/CH4 chemical kinetic model currently under development at the University of Galway. The effect of the updated kinetic data for ĊH3 + ṄH2 on model predicted NH3/CH4 fuel reactivity is elucidated.

Publisher

Elsevier

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CC BY

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School of Biological and Chemical Sciences (Scholarly Articles)