Here, the kinetics of the concerted [3 + 2] cycloaddition reaction between the [Mo₃(μ₃‐S)(μ‐S)₃Cl₃(dmen)₃]⁺ (dmen = N,N′‐dimethyl‐ethylenediamine) ([1]⁺) cluster and various alkynes to form dithiolene derivatives is thoroughly studied, with measurements at different temperatures and pressures allowing the determination of the free energies and volumes of activation. These parameters, together with the available single‐crystal X‐ray diffraction structures, are used to test a number of commonly used density functional theory (DFT) methods from Jacob's ladder, as well as the effects associated with the size of the basis sets, the way in which solvent effects are taken into account, or the inclusion of dispersion effects. Overall, a protocol that leads to average deviations between experimental and computed ΔV^‡ and ΔG^‡ values similar to the uncertainty of the experimental measurements is obtained.

中文翻译：

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DFT方法的基准测试，使用实验性自由能和活化体积将炔烃环化成立方Mo3S4团簇

在这里，一致的[3 + 2]环加成的[沫之间反应的动力学₃（μ ₃ -S）（μ-S）₃氯₃（DMEN）₃ ] ⁺（DMEN = N，N- ' -二甲基乙二胺）（[ 1 ] ⁺）深入研究了团簇和各种炔烃以形成二硫代烯衍生物，并在不同温度和压力下进行了测量，从而确定了活化能和自由能。这些参数与可用的单晶X射线衍射结构一起用于测试Jacob's阶梯的许多常用密度泛函理论（DFT）方法以及与基集大小相关的影响，考虑溶剂效应的方式，或包含分散效应。总的来说，获得了导致实验和计算出的ΔV ^‡和ΔG ^‡值之间出现平均偏差的方案，类似于实验测量的不确定度。