Quintal Miriam M, Karton Amir, Iron Mark A, Boese A Daniel, Martin Jan M L
Department of Organic Chemistry, Weizmann Institute of Science, 76100 Rehovot, Israel.
J Phys Chem A. 2006 Jan 19;110(2):709-16. doi: 10.1021/jp054449w.
The performance of a wide variety of DFT exchange-correlation functionals for a number of late-transition-metal reaction profiles has been considered. Benchmark ab-initio reference data for the prototype reactions Pd + H2, Pd + CH4, Pd + C2H6 (both C-C and C-H activation), and Pd + CH3Cl are presented, while ab-initio data of lesser quality were obtained for the catalytic hydrogenation of acetone and for the low-oxidation-state and high-oxidation-state mechanisms of the Heck reaction. "Kinetics" functionals such as mPW1K, PWB6K, BB1K, and BMK clearly perform more poorly for late-transition-metal reactions than for main-group reactions, as well as compared to general-purpose functionals. There is no single "best functional" for late-transition-metal reactions, but rather a cluster of several functionals (PBE0, B1B95, PW6B95, and TPSS25B95) that perform about equally well; if main-group thermochemical performance is additionally considered, then B1B95 and PW6B95 emerge as the best performers. TPSS25B95 and TPSS33B95 offer attractive performance compromises if weak interactions and main-group barrier heights, respectively, are also important. In the ab-initio calculations, basis set superposition errors (BSSE) can be greatly reduced by ensuring that the metal spd shell has sufficient radial flexibility in the high-exponent range. Optimal HF percentages in hybrid functionals depend on the class of systems considered, increasing from anions to neutrals to cations to main-group barrier heights; transition-metal barrier heights represent an intermediate situation. The use of meta-GGA correlation functionals appears to be quite beneficial.
我们考察了多种密度泛函理论（DFT）交换关联泛函对一些晚期过渡金属反应路径的性能。给出了原型反应Pd + H₂、Pd + CH₄、Pd + C₂H₆（包括C - C和C - H活化）以及Pd + CH₃Cl的基准从头算参考数据，同时还获得了丙酮催化氢化反应以及Heck反应的低氧化态和高氧化态机理的质量稍逊的从头算数据。诸如mPW1K、PWB6K、BB1K和BMK等“动力学”泛函在晚期过渡金属反应中的表现明显比在主族反应中差，与通用泛函相比也是如此。对于晚期过渡金属反应，没有单一的“最佳泛函”，而是有一组性能相当的泛函（PBE0、B1B95、PW6B95和TPSS25B95）；如果额外考虑主族热化学性能，那么B1B95和PW6B95表现最佳。如果弱相互作用和主族能垒高度分别也很重要，那么TPSS25B95和TPSS33B95提供了有吸引力的性能折衷方案。在从头算计算中，通过确保金属spd壳层在高指数范围内具有足够的径向灵活性，可以大大降低基组叠加误差（BSSE）。杂化泛函中的最佳HF百分比取决于所考虑的系统类别，从阴离子到中性分子再到阳离子，然后到主族能垒高度逐渐增加；过渡金属能垒高度代表一种中间情况。使用meta - GGA关联泛函似乎非常有益。
