Rediscovering the Wheel. Thermochemical Analysis of Energetics of the Aromatic Diazines.
Rediscovering the Wheel. Thermochemical Analysis of Energetics of the Aromatic Diazines.
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重新发现轮子。
DOI：
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发表时间：
2012
影响因子：
5.7
通讯作者：
J. Liebman
中科院分区：
文献类型：
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作者：
S. P. Verevkin;V. N. Emel’yanenko;R. Notario;M. Roux;J. Chickos;J. Liebman
已测量并重新评估了嘧啶、吡嗪和哒嗪的热化学性质，以提供基准质量结果。从燃烧量热法和蒸汽压测量中获得了新的内部一致的ΔFHm(G)数据集。重新计算了母体二氮杂环化合物的气相和凝聚相生成热，并与目前采用高精度第一原理方法G3、G4、CBS-APNO、W1(RO)的理论计算结果进行了比较。直接从H298生成理论ΔFHm(G)的简单“修正雾化程序”已经过测试，并被推荐作为一种替代使用键分离和等键反应模型的方法，用于含有一到三个氮原子的有机环和杂环化合物。
Thermochemical properties of pyrimidine, pyrazine, and pyridazine have been measured and re-evaluated to provide benchmark quality results. A new internally consistent data set of ΔfHm(g) has been obtained from combustion calorimetry and vapor pressure measurements. The gas and condensed phase enthalpies of formation of the parent diazines have been re-evaluated, and the results were compared to current theoretical calculations using the highly accurate first-principles methods: G3, G4, CBS- APNO, W1(RO). Simple "corrected atomization procedures" to derive theoretical ΔfHm(g) directly from the enthalpies H298 have been tested and recommended as an alternative to using the bond separation and isodesmic reaction models for organic cyclic and heterocyclic compounds containing one to three nitrogen atoms.