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/(molK), and 1.20 cal/(molK) 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.

中文翻译：

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更新了可再生运输燃料的热化学：缩醛和醚，其自由基和过氧物质的新基团和基团值

我们提供了适合燃烧建模的醚，聚醚和乙缩醛的气相热化学新的组和组值。我们的研究包括燃料种类，它们的主要自由基，过氧自由基和氢过氧化物种类。总共有45种用于14个组的参数化，其中六个是新引入的。目前，在理论上将DLPNO-CCSD（T）/ CBS（cc-pVTZ，cc-PVQZ）// B3LYP-D3BJ / def2-TZVP的计算热化学与文献中的热化学结合在一起。根据量子力学结果验证新的基团值得出的偏差为1.22 kcal / mol，2.36 cal /（mol K）和1.20 cal /（molK）分别用于形成热，标准熵和热容。新的热化学用最新的OME2和OME3化学动力学模型进行了测试，该模型对中间温度范围内的更新值显示出很大的敏感性。这凸显了在未来的氧化甲基醚（OMEs）和OME相关结构的化学动力学建模研究中使用更新的热化学的重要性。