卤代乙炔类化合物XCCY [X，Y = H，F，Cl]的生成热：基组极限从头算结果和热化学分析
The heats of formation of the haloacetylenes XCCY [X, Y = H, F, Cl]: basis set limit ab initio results and thermochemical analysis
摘要：
用最近的W1和W2从头计算热化学方法计算卤代乙炔的生成热。这些计算涉及CCSD和CCSD（T）耦合团簇方法、spdfgh质量的基组、单粒子基组极限的外推、内壳层关联、标量相对论效应和（在相关的情况下）一阶自旋轨道耦合的贡献。使用W2理论确定的生成热为：\hof（HCCH）= 54.48 kcal/mol，\hof（HCCF）= 25.15 kcal/mol，\hof（FCCF）= 1.38 kcal/mol，\hof（HCCCl）= 54.83 kcal/mol，\hof（ClCCCl）= 56.21 kcal/mol，和\hof（FCCCl）= 28.47 kcal/mol。在W1理论水平上得到了乙炔的氢化焓和失稳能。因此，我们发现乙炔的下列去稳定化顺序：FCCF $>$ ClCCF $>$ HCCF $>$ ClCCCl $>$ HCCCl $>$ HCCH。通过结合W1理论和等键反应，我们表明，普遍接受的1，2-二氯乙烷的生成热应修订为-31.8 $\pm$ 0.6千卡/摩尔，在很好的协议，与最近的批判性评价审查。分析了G2、G3、G3 X和CBS-QB 3理论等复合热化学方案的性能。
英文摘要：
The heats of formation of haloacetylenes are evaluated using the recent W1 and W2 ab initio computational thermochemistry methods. These calculations involve CCSD and CCSD(T) coupled cluster methods, basis sets of up to spdfgh quality, extrapolations to the one-particle basis set limit, and contributions of inner-shell correlation, scalar relativistic effects, and (where relevant) first-order spin-orbit coupling. The heats of formation determined using W2 theory are: \hof(HCCH) = 54.48 kcal/mol, \hof(HCCF) = 25.15 kcal/mol, \hof(FCCF) = 1.38 kcal/mol, \hof(HCCCl) = 54.83 kcal/mol, \hof(ClCCCl) = 56.21 kcal/mol, and \hof(FCCCl) = 28.47 kcal/mol. Enthalpies of hydrogenation and destabilization energies relative to acetylene were obtained at the W1 level of theory. So doing we find the following destabilization order for acetylenes: FCCF $>$ ClCCF $>$ HCCF $>$ ClCCCl $>$ HCCCl $>$ HCCH. By a combination of W1 theory and isodesmic reactions, we show that the generally accepted heat of formation of 1,2-dichloroethane should be revised to -31.8$\pm$0.6 kcal/mol, in excellent agreement with a very recent critically evaluated review. The performance of compound thermochemistry schemes such as G2, G3, G3X and CBS-QB3 theories has been analyzed.
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