Mechanistic investigations at the density functional theory level of organic and organometallic reactions in solution are now broadly accessible and routinely implemented to complement experimental investigations. The selection of an appropriate functional among the plethora of developed ones is the first challenge on the way to reliable energy barrier calculations. To provide guidelines for the choice of an initial and reliable computational level, the performances of commonly used non-empirical (PBE, PBE0, PBE0-DH) and empirical density functionals (BLYP, B3LYP, B2PLYP) were evaluated relative to experimental activation enthalpies. Most reactivity databases to assess density functional performances are primarily based on high level calculations, here a set of experimental activation enthalpies of organic and organometallic reactions performed in solution were selected from the literature. As a general trend, the non-empirical functionals outperform the empirical ones. The most accurate energy barriers are obtained with hybrid PBE0 and double-hybrid PBE0-DH density functionals, both providing similar performance. Regardless of the functional under consideration, the addition of the GD3-BJ empirical dispersion correction does not enhance the accuracy of computed energy barriers.

中文翻译：

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溶液中的计算能垒与实验能垒：密度泛函近似类型的影响


溶液中有机和有机金属反应的密度泛函理论水平的机理研究现在可以广泛使用并常规实施，以补充实验研究。在众多已开发的函数中选择合适的函数是可靠的能量势垒计算的第一个挑战。为了为选择初始和可靠的计算水平提供指导，常用的非经验（PBE、PBE0、PBE0-DH）和经验密度泛函（BLYP、B3LYP、B2PLYP）的性能相对于实验活化焓进行了评估。大多数评估密度泛函性能的反应性数据库主要基于高级计算，这里从文献中选择了一组在溶液中进行的有机和有机金属反应的实验活化焓。作为总体趋势，非经验泛函优于经验泛函。最准确的能量势垒是通过混合 PBE0 和双混合 PBE0-DH 密度泛函获得的，两者都提供相似的性能。无论考虑什么功能，添加 GD3-BJ 经验色散校正都不会提高计算能垒的准确性。