Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling
Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling
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DOI：
10.1021/acs.iecr.1c03076
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发表时间：
2021-10-22
影响因子：
4.2
通讯作者：
West, Richard H.
中科院分区：
文献类型：
--
作者：
Farina, David S., Jr.;Sirumalla, Sai Krishna;West, Richard H.
使用自动化高保真热化学工作流程计算16813卤化碳的标准焓、熵和热容。该工作流程在密度泛函紧束缚（DFTB）水平生成构象，优化几何形状，计算谐波频率，并在DFT水平进行1D受阻转子扫描，并在高斯4（G4）水平计算电子能量。计算的400个分子的生成谱与参考文献显示出良好的一致性，但大多数计算的物种在文献中没有参考。因此，这项工作提出了G4-计算热化学的数千种新的卤代烃。这个新的数据集用于训练反应机制生成器（RMG）框架内的基团加和值和氢键增量基团的广泛集合。平均而言，新的组值估计卤代烃的标准沸点对卤代烃燃烧的自动化机制生成的重要贡献，本研究提供了其G4值的3千卡/摩尔内的热化学。一个数以千计的新的卤化物种的数据，并提出了一个自洽的一套卤素基团的加和值。
Standard enthalpies, entropies, and heat capacities are calculated for 16 813 halocarbons using an automated high-fidelity thermochemistry workflow. This workflow generates conformers at density functional tight-binding (DFTB) level, optimizes geometries, calculates harmonic frequencies, and performs 1D hindered rotor scans at DFT level, and computes electronic energies at a Gaussian 4 (G4) level. The computed enthalpies of formation for 400 molecules show good agreement with literature references, but the majority of the calculated species have no reference in the literature. Thus, this work presents G4-computed thermochemistry for thousands of novel halocarbons. This new data set is used to train an extensive ensemble of group additivity values and hydrogen bond increment groups within the Reaction Mechanism Generator (RMG) framework. On average, the new group values estimate standard enthalpies for halogenated hydrocarbons significant contribution toward automated mechanism generation of halocarbon combustion, this research provides thermochemical within 3 kcal/mol of their G4 values. A data for thousands of novel halogenated species and presents a self-consistent set of halogen group additivity values.