A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.
A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.
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DOI：
10.1002/jcc.21729
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发表时间：
2011-06
影响因子：
3
通讯作者：
Dannenberg, J. J.
中科院分区：
文献类型：
--
作者：
Plumley, Joshua A.;Dannenberg, J. J.
我们评估了九个泛函的性能（B3LYP，M05，M05-2X，M06，M06-2X，B2PLYP，B2PLYPD，X3LYP，B 97 D和MPWB 1 K）与复杂度范围从6- 31 G（d）到aug-cc-pV 5 Z的16个基组组合，用于计算H-键合的水二聚体的目标是定义哪些组合的泛函和基组提供了一个组合的经济性和准确性的H-键合系统。我们比较了最好的非DFT分子轨道计算和实验结果的结果。几个较小的基组导致定性不正确的几何形状优化时，正常的势能面（PES）。当在平衡校正PES上执行优化时，该问题消失。对于不同的泛函，用最大基组计算的ΔE在-4.42（B 97 D）到-5.19（B2 PLYPD）kcal/mol之间变化。小的基组通常比大的基组预测更强的相互作用。我们发现，由于误差补偿，当与预测与最大基组的弱相互作用的泛函相结合时，较小的基组给出了最好的结果（与实验和高水平非DFT MO计算相比）。由于许多应用是复杂的系统，需要经济的计算，我们建议以下功能/基组组合，以增加的复杂性和成本：1）D95（d，p）与B3 LYP，B 97 D，M06或MPWB 1 k; 2）6- 311 G（d，p）与B3 LYP; 3）D95++（d，p）与B3 LYP，B 97 D或MPWB 1 K; 5）aug-cc-pVDZ与M05-2X、M06-2X或X3 LYP。
We evaluate the performance of nine functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-DFT molecular orbital calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise corrected PES. The calculated ΔE's with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, due to error compensation, the smaller basis sets gave the best results (in comparison to experimental and high level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. Since many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: 1) D95(d,p) with B3LYP, B97D, M06 or MPWB1k; 2) 6-311G(d,p) with B3LYP; 3) D95++(d,p) with B3LYP, B97D or MPWB1K; 4)6-311++G(d,p) with B3LYP or B97D; and 5) aug-cc-pVDZ with M05-2X, M06-2X or X3LYP.
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影响因子：
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