A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties. To address the scarcity of accurate experimental data, theoretical calculations can be used. The accuracy of these quantum chemistry methods for determination of thermodynamic properties can be improved by making use of empirical correction methods, such as the isodesmic bond additivity correction (BAC) method. In this work, ab initio calculations for a set of 371 molecules have been performed to determine a new set of BACs for the CBS‐QB3 level of theory. For each of these molecules also accurate experimental data, that is with an experimental uncertainty less than 3 kJ mol⁻¹, is available. This broad dataset of hydrocarbons and heteroatomic compounds contains (non)cyclic molecules with a wide range of functional groups consisting of hydrogen, carbon, oxygen, nitrogen, and sulfur. The new set of 26 BAC parameters is obtained via linear regression analysis, minimizing the differences between experimental and corrected CBS‐QB3 values. The CBS‐QB3 method combined with BACs succeeds in approximating the experimental standard enthalpy of formation at 298 K with an accuracy of 4 kJ mol⁻¹ for almost all species. The BACs reduce the mean absolute deviation for the complete dataset from 5.65 to 2.37 kJ mol⁻¹, corresponding to a decrease of the root mean square deviation from 6.95 to 3.00 kJ mol⁻¹.

中文翻译：

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CBS-QB3的键加和校正修正了包含H，C，O，N和S的物质形成的标准焓

产生详细的基本动力学模型的前提是要获得准确的热力学性质。为了解决精确实验数据的不足，可以使用理论计算。这些量子化学方法测定热力学性质的准确性可以通过使用经验校正方法（例如等电键加和校正（BAC））来提高。在这项工作中，已经针对371个分子进行了从头算计算，以确定了CBS-QB3理论水平的一组新的BAC。对于这些分子中的每一个，也可以获得准确的实验数据，即实验不确定度小于3 kJ mol ^-1可用。碳氢化合物和杂原子化合物的广泛数据集包含具有广泛官能团的（非）环状分子，所述官能团由氢，碳，氧，氮和硫组成。通过线性回归分析获得了一组新的26个BAC参数，从而最大程度地减少了实验值和校正后的CBS-QB3值之间的差异。结合BAC的CBS-QB3方法成功地以几乎所有物种的4 kJ mol ^-1的精度成功地逼近了298 K时的实验标准生成焓。BAC将完整数据集的平均绝对偏差从5.65降低到2.37 kJ mol ^-1，对应于均方根偏差从6.95降低到3.00 kJ mol ^-1。