Updated thermochemistry for renewable transportation fuels: New groups and group values for acetals and ethers, their radicals, and peroxy species

• Published in: International journal of chemical kinetics 2021-02, Vol.53 (2), p.299-307
• Main Authors: Döntgen, Malte, Kopp, Wassja A., vom Lehn, Florian, Kröger, Leif C., Pitsch, Heinz, Leonhard, Kai, Heufer, K. Alexander
• Format: Article
• Language: English
• Subjects: ab initio thermochemistry; Acetals; Ethers; group additivity theory; Heat of formation; Modelling; oxymethylene ethers; Parameterization; Peroxy radicals; Polyethers; Quantum mechanics; Thermochemistry
• ISSN: 0538-8066; 1097-4601
• DOI: 10.1002/kin.21443

We present new groups and group values for the gas‐phase thermochemistry of ethers, polyethers, and acetals suited for combustion modeling. Our investigation comprises fuel species, their primary radicals, peroxy radicals, and hydroperoxide species. In total, 45 species are used for the parameterization of 14 groups, six of which are newly introduced here. Presently, calculated thermochemistry at the DLPNO‐CCSD(T)/CBS(cc‐pVTZ, cc‐PVQZ) // B3LYP‐D3BJ/def2‐TZVP level of theory is combined with thermochemistry from the literature. Validation of the new group values against the quantum mechanical results gives deviations of 1.22 kcal/mol, 2.36 cal/(mol·K), and 1.20 cal/(mol·K) for heats of formation, standard entropies, and heat capacities, respectively. The new thermochemistry is tested with a recent OME2 and OME3 chemical kinetic model, which shows large sensitivities to the updated values in the intermediate temperature regime. This highlights the importance of using updated thermochemistry in future chemical kinetic modeling studies of oxygenated methyl ethers (OMEs) and OME‐related structures.