Comparative Study of Single and Double Hybrid Density Functionals for the Prediction of 3d Transition Metal Thermochemistry
Comparative Study of Single and Double Hybrid Density Functionals for the Prediction of 3d Transition Metal Thermochemistry
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DOI：
10.1021/ct300455e
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发表时间：
2012-11-01
影响因子：
5.5
通讯作者：
Wilson, Angela K.
中科院分区：
文献类型：
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作者：
Jiang, Wanyi;Laury, Marie L.;Wilson, Angela K.
13个密度泛函，包括混合GGA，混合-meta-GGA，和双杂化泛函，结合相关性一致的基组的性能，已被评估为预测的气相生成的三维过渡金属的分子与通用的键合功能的一大套。在所研究的方法中，混合B 97 -1功能和双混合功能mPW 2-PLYP表现出最佳的整体性能，与实验数据的平均绝对偏差（MAD）分别为7.2和7.3 kcal mol（-1）。对于单参比分子，其中动态相关占主导地位，杂交泛函B 97 -1，B 98，和欧米茄B 97 X和双杂交泛函B2-PLYP，B2 GP-PLYP，和mPW 2-PLYP的结果产生最小的偏差，从实验的形成。对于含羰基金属配合物的热力学性质的预测，B 97 -1和mPW 2-PLYP是最有希望的泛函。当考虑分子的尺寸时，B 97 -1和B 98的预测结果优于mPW 2-PLYP，而mPW 2-PLYP对较大分子的预测结果最低。
The performance of 13 density functionals, including hybrid-GGA, hybrid-meta-GGA, and double-hybrid functionals, in combination with the correlation consistent basis sets, has been evaluated for the prediction of gas phase enthalpies of formation for a large set of 3d transition-metal-containing molecules with versatile bonding features. Of the methods studied, the hybrid B97-1 functional and the double hybrid functional mPW2-PLYP exhibit the best overall performance with mean absolute deviations (MAD) from experimental data of 7.2 and 7.3 kcal mol(-1), respectively. For single reference molecules, where dynamic correlation predominates, the results of the hybrid functionals B97-1, B98, and omega B97X and the double hybrid functionals B2-PLYP, B2GP-PLYP, and mPW2-PLYP yield the smallest deviations from the experimental enthalpies of formation. For the prediction of thermodynamic properties of coordination complexes including metal carbonyls, B97-1 and mPW2-PLYP are the most promising functionals of those investigated When the size of the molecule is considered, B97-1 and B98 outperform mPW2-PLYP for diatomics and triatomics, while mPW2-PLYP yields the lowest MAD for larger molecules.