The secondary chemistry of synthetic fuel oxymethylene ethers unraveled: Theoretical and kinetic modeling of methoxymethyl formate and formic anhydride decomposition

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

“…Finally, with the increasing amount of high-level quantum chemical data for OMEs and OME-derived species becoming available in the literature, ,,,,− it would be interesting to compare the estimation methods developed in this work with novel methods, such as machine learning. The performance of kinetic group additivity, which can be seen as a simplified version of machine learning, indicates the potential of machine learning tools such as deep learning.…”

“…For the quantum chemical calculations, the software package Gaussian 16 Revision C.01 is used. The electronic structure calculations are performed at the CBS-QB3 level of theory, which is developed by Montgomery et al The CBS-QB3 level of theory has been selected to be consistent with earlier work performed within our research group. ,,, Starting from an initial “guess” geometry, the lowest energy conformer is determined iteratively by geometry optimization combined with 1-dimensional rotational scans around all dihedral angles present in the molecule. These rotational scans, which are performed in steps of 10° sampling the complete rotation, are performed at the B3LYP/6-31G­(d) − level of theory.…”

An experimental and kinetic modeling study on the low-temperature oxidation of oxymethylene ether-2 (OME-2) by means of stabilized cool flames

“…S12). Validation of the kinetic model against pyrolysis data was extensively performed in our previous studies [15,17,28] and is identical for this new model as the chemistry related to pyrolysis was not adapted.…”

“…The kinetic model developed by De Ras et al [15] for pyrolysis and oxidation of OME-2 is the only available model based on first principles, which outperformed the other models from the literature. In the meantime, two additional studies were published by Van Geem and co-workers to refine this OME-2 model with new fundamental insights into the initial unimolecular decomposition pathways via carbene chemistry [17] and the radical decomposition of methoxymethyl formate and formic anhydride [28], i.e., important intermediates formed during pyrolysis and oxidation of OMEs.…”

Unraveling the carbene chemistry of oxymethylene ethers: Experimental investigation and kinetic modeling of the high-temperature pyrolysis of OME-2

“…The thermal decomposition chemistry is an essential aspect of every combustion mechanism. Although several experimental studies have been published on the pyrolysis of dimethyl ether (DME) [10][11][12] and dimethoxymethane (DMM, OME-1) [13][14][15] , there is scarcity in reliable pyrolysis data for larger OMEs [16,17] , to be used for kinetic model validation. Cai et al [18] reported on the autoignition of OME-2, OME-3 and OME-4 with air by performing ignition delay time measurements in a shock-tube for different equivalence ratios and total pressures.…”