The gas-phase enthalpy of formation (ΔHf) plays a fundamental role in predicting reaction thermodynamics and constructing kinetic models. With advances in computational power and method development, chemically accurate quantum chemistry methods that can predict ΔHf values for small molecules are available; however, large molecules are still out of reach. Increment theories provide a means of extending the prediction capability of high-level methods by decomposing the molecular ΔHf into the additive contributions from individual atoms, bonds, groups, or components. Here, we introduce a novel component increment theory, topology-automated force-field interaction component increment theory (TCIT), in which all component contributions are derived exclusively from Gaussian-4 (G4) results for algorithmically generated model compounds. In a benchmark evaluation of noncyclic compounds from the Pedley, Naylor, and Kline experimental ΔHf dataset, TCIT exhibits consistently lower signed and absolute errors compared with the conventional Benson group increment theory (BGIT). These results pave the way for future extensions of TCIT to ring-containing, ionic, and radical species for which experimental data scarcity currently limits the application of BGIT.

中文翻译：

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用于预测生成焓的自洽分量递增理论。

气相生成焓（ΔHf）在预测反应热力学和构建动力学模型中起着基本作用。随着计算能力和方法开发的进步，可以预测小分子ΔHf值的化学精确的量子化学方法已经可用。但是，大分子仍然遥不可及。增量理论通过将分子ΔHf分解为单个原子，键，基团或成分的累加贡献，提供了扩展高级方法的预测能力的方法。在这里，我们介绍了一种新颖的构件增量理论，即拓扑自动力场相互作用构件增量理论（TCIT），其中所有构件的贡献均来自于算法生成的模型化合物的高斯4（G4）结果。在对来自Pedley，Naylor和Kline实验ΔHf数据集的非环状化合物进行的基准评估中，与传统的Benson基团增量理论（BGIT）相比，TCIT始终显示出较低的正负号和绝对误差。这些结果为将来将TCIT扩展到含环的，离子的和自由基的物质铺平了道路，目前，缺乏实验性数据限制了BGIT的应用。