Exploring the Ab Initio Kinetics of Trimethyl Phosphite

Trimethyl phosphite (TMPI) is an organophosphorus compound of growing interest in the contexts of fire safety and energetic materials. Yet, its gas-phase combustion kinetics remain largely underexplored. We develop a TMPI kinetic mechanism from first-principles quantum chemistry and master-equation (RRKM/MESS) calculations, supported by reactive molecular dynamics (ReaxFF-MD) to map early time bond activation and product growth. The potential-energy surfaces include C–O and P–O homolysis, hydrogen-atom abstraction (HAA) by Ḣ, ȮH, HȮ2, ĊH3, and CH3Ȯ, and O2, intramolecular H-transfer, and key association or isomerization steps. Thermochemistry (ΔHf°, S, cp) and NASA polynomials are provided for all P-bearing intermediates. The model reproduces the expected Arrhenius behavior of ignition delay times (IDTs) for TMPI/air across a temperature range of 900–1500 K and pressures of 1 and 10 bar, with φ values ranging from 0.5 to 2.0. Increasing temperature and pressure shorten the IDT, with richer mixtures igniting faster. Sensitivity and flux analyses identify high-temperature chain branching (H + O2 ⇌ O + OH) and control of the HO2/OH pools as primary rate-controlling features, while TMPI–radical reactions that convert radicals to stable products inhibit ignition. Flux maps show HAA-initiated TMPI_R as the universal entry to the radical pool and reveal PO2 as a central hub that feeds PO, HOPO/HOPO2, and ultimately PO3. Hybrid NVT+NVE MD trajectories further indicate an earlier onset of decomposition under adiabatic conditions, consistent with the rapid amplification of radicals once local hot spots are not thermostat-damped. The resulting mechanism and thermochemical set provide a consistent foundation for modeling phosphite oxidation and for comparing phosphite, phosphate, and phosphonate chemistries in fire-inhibition strategies.