We have developed a new database of structures and bond energies of 59 noble‐gas‐containing molecules. The structures were calculated by CCSD(T)/aug‐cc‐pVTZ methods and the bond energies were obtained using the CCSD(T)/complete basis set method. Many wavefunction‐based and density functional theory methods have been benchmarked against the 59 accurate bond energies. Our results show that the MPW1B95, B2GP‐PLYP, and DSD‐BLYP functionals with the aug‐cc‐pVTZ basis set excel in predicting the bond energies of noble‐gas molecules with mean unsigned errors (MUEs) of 2.0 to 2.1 kcal/mol. When combinations of Dunning's basis sets are used, the MPW1B95, B2GP‐PLYP, DSD‐BLYP, and BMK functionals give significantly lower MUEs of 1.6 to 1.9 kcal/mol. Doubly hybrid methods using B2GP‐PLYP and DSD‐BLYP functionals and MP2 calculation also provide satisfactory accuracy with MUEs of 1.4 to 1.5 kcal/mol. If the Ng bond energies and the total atomization energies of a group of 109 main‐group molecules are considered at the same time, the MPW1B95/aug‐cc‐pVTZ single‐level method (MUE = 2.7 kcal/mol) and the B2GP‐PLYP and DSD‐PLYP functionals with combinations of basis sets or using the doubly hybrid method (MUEs = 1.9‐2.2 kcal/mol) give the overall best result.

中文翻译：

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含稀有气体分子的键能的新数据库和基准

我们已经开发了一个新的59个含稀有气体分子的结构和键能的数据库。通过CCSD（T）/ aug-cc-pVTZ方法计算结构，并使用CCSD（T）/完全基集方法获得键能。许多基于波动函数和密度泛函理论的方法已经针对59种精确的键能进行了基准测试。我们的结果表明，具有aug-cc-pVTZ基集的MPW1B95，B2GP-PLYP和DSD-BLYP功能在预测平均无符号误差（MUE）为2.0至2.1 kcal / mol的稀有气体分子的键能方面表现出色。当使用Dunning的基础集组合时，MPW1B95，B2GP-PLYP，DSD-BLYP和BMK功能会显着降低1.6至1.9 kcal / mol的MUE。使用B2GP-PLYP和DSD-BLYP功能以及MP2计算的双重混合方法还可以提供令人满意的精度，其MUE为1.4至1.5 kcal / mol。如果同时考虑一组109个主族分子的Ng键能和总雾化能，则MPW1B95 / aug-cc-pVTZ单能级方法（MUE = 2.7 kcal / mol）和B2GP-将PLYP和DSD-PLYP功能与基集组合或使用双重混合方法（MUE = 1.9-2.2 kcal / mol）可获得总体最佳结果。