Design of density functionals that are broadly accurate for thermochemistry, thermochemical kinetics, and nonbonded interactions.
Design of density functionals that are broadly accurate for thermochemistry, thermochemical kinetics, and nonbonded interactions.
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DOI：
10.1021/jp050536c
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发表时间：
2005-06
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影响因子：
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通讯作者：
Yan Zhao;D. Truhlar
中科院分区：
文献类型：
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作者：
Yan Zhao;D. Truhlar
本文发展了两个新的混合偏交换-关联泛函，用于热化学、热化学动力学和非键相互作用。新泛函命名为PW6B95(基于Perdew-Wang-91交换和Becke-95关联的6参数泛函)和PWB6K(基于Perdew-Wang-91交换和Becke-95关联的6参数动力学泛函)。将所得到的方法与MGAE109/3主族原子化能数据库、IP13/3电离势数据库、EA13/3电子亲和力数据库、HTBH38/4和NHTBH38/04氢转移和非氢转移势垒高度数据库、HB6/04氢键数据库、CT7/04电荷转移络合物数据库、DI6/04偶极相互作用数据库、WI7/05弱相互作用数据库以及新的PPS5/05 pi-pi堆积相互作用数据库进行了比较评估。通过对各种方法的评价和比较，基于平均无符号误差分析，我们得出以下结论：(1)PW6B95、MPW1B95、B98、B97-1和TPSS1KCIS方法对于热化学和非键相互作用的结合给出了最好的结果。(Ii)PWB6K、MPWB1K、BB1K、MPW1K和MPW1B95对热化学动力学和非键相互作用的结合效果最好。(3)对于非键相互作用，PWB6K优于MP2方法。(Iv)PW6B95给出的主要基团共价键能量的误差仅为0.41kcal(以MGAE109数据库的每个键的平均无符号误差(MUEPB)衡量)，而次佳方法为0.56kcal/mol，B3LYP为0.92kcal/mol。
This paper develops two new hybrid meta exchange-correlation functionals for thermochemistry, thermochemical kinetics, and nonbonded interactions. The new functionals are called PW6B95 (6-parameter functional based on Perdew-Wang-91 exchange and Becke-95 correlation) and PWB6K (6-parameter functional for kinetics based on Perdew-Wang-91 exchange and Becke-95 correlation). The resulting methods were comparatively assessed against the MGAE109/3 main group atomization energy database, against the IP13/3 ionization potential database, against the EA13/3 electron affinity database, against the HTBH38/4 and NHTBH38/04 hydrogen-transfer and non-hydrogen-transfer barrier height databases, against the HB6/04 hydrogen bonding database, against the CT7/04 charge-transfer complex database, against the DI6/04 dipole interaction database, against the WI7/05 weak interaction database, and against the new PPS5/05 pi-pi stacking interaction database. From the assessment and comparison of methods, we draw the following conclusions, based on an analysis of mean unsigned errors: (i) The PW6B95, MPW1B95, B98, B97-1, and TPSS1KCIS methods give the best results for a combination of thermochemistry and nonbonded interactions. (ii) PWB6K, MPWB1K, BB1K, MPW1K, and MPW1B95 give the best results for a combination of thermochemical kinetics and nonbonded interactions. (iii) PWB6K outperforms the MP2 method for nonbonded interactions. (iv) PW6B95 gives errors for main group covalent bond energies that are only 0.41 kcal (as measured by mean unsigned error per bond (MUEPB) for the MGAE109 database), as compared to 0.56 kcal/mol for the second best method and 0.92 kcal/mol for B3LYP.