Hall-Atwater Laboratories of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, USA.
J Phys Chem A. 2013 Jun 6;117(22):4726-30. doi: 10.1021/jp404158v. Epub 2013 May 28.
Inexpensive ab initio procedures that employ homologous sequences of isodesmic reactions for the calculation of enthalpies of formation of moderate-sized organic molecules were tested with benzene, naphthalene, phenanthrene, and triphenylene. Two size-consistent adjustable parameters were found to bring the calculated values within the uncertainty of the experimental values. These procedures were then applied to C20H10 (corannulene) and C60 (buckminsterfullerene). The results, specifically, Δ(f)H(298)(0)(C20H10) = 484 ± 4 kJ mol(-1) and Δ(f)H(298)(0)(C60) = 2531 ± 15 kJ mol(-1), are in excellent agreement with both the recent definitive W1h calculations of Karton et al. for corannulene [Δ(f)H(298)(0)(C20H10) = 485.2 ± 7.9 kJ mol(-1)] and their estimated value for buckminsterfullerene [Δ(f)H(298)(0)(C60) = 2521.6 ± 13.6 kJ mol(-1)] ( J. Phys. Chem. A 2013, 117, 1834-1842). We support their conclusion that the experimental values should be reexamined.
我们测试了采用同系反应的焓生成值计算中等大小有机分子的廉价从头计算程序，这些反应的焓生成值可通过同系反应计算得到。我们找到了两个大小一致的可调节参数，将计算值纳入实验值的不确定度范围内。然后，我们将这些程序应用于 C20H10（corannulene）和 C60（buckminsterfullerene）。具体而言，Δ(f)H(298)(0)(C20H10) = 484 ± 4 kJ mol(-1)和Δ(f)H(298)(0)(C60) = 2531 ± 15 kJ mol(-1)的结果与 Karton 等人最近对 corannulene 的 W1h 计算[Δ(f)H(298)(0)(C20H10) = 485.2 ± 7.9 kJ mol(-1)]以及他们对 buckminsterfullerene 的估计值[Δ(f)H(298)(0)(C60) = 2521.6 ± 13.6 kJ mol(-1)]（J. Phys. Chem. A 2013, 117, 1834-1842）非常吻合。我们支持他们的结论，即应该重新检查实验值。
