Benchmark database of barrier heights for heavy atom transfer, nucleophilic substitution, association, and unimolecular reactions and its use to test theoretical methods.
Benchmark database of barrier heights for heavy atom transfer, nucleophilic substitution, association, and unimolecular reactions and its use to test theoretical methods.
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DOI：
10.1021/jp045141s
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发表时间：
2005-02
期刊：
影响因子：
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通讯作者：
Yan Zhao;Núria González-García;D. Truhlar
中科院分区：
文献类型：
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作者：
Yan Zhao;Núria González-García;D. Truhlar
使用Weizmann 1计算开发了19个非氢转移反应的正向和反向势垒高度的基准数据库，并对新数据库和旧数据库的氢原子转移反应测试了29种DFT方法和6种从头算波函数理论（WFT）方法。在测试的混合DFT方法没有动能密度，MPW 1 K是最准确的模型计算势垒高度。在测试的混合Meta DFT方法中，BB 1 K和MPWB 1 K是计算势垒高度的两个最准确的模型。总体而言，结果表明BB 1 K和MPW 1 K是计算势垒高度的两种最佳DFT方法，其次是MPW 1 K，MPWKCIS 1 K，B1 B 95，MPW 1B 95，BH和HLYP，B 97 -2，mPW 1 PW 91和B 98。流行的B3 LYP方法的平均无符号误差比BB 1 K大四倍。在测试的方法中，QCISD（T）是计算势垒高度的最佳从头算WFT方法，QCISD是第二好的，但QCISD优于BB 1 K，MPWB 1 K，MPWKCIS 1 K和MPW 1 K方法。
A benchmark database of forward and reverse barrier heights for 19 non-hydrogen-transfer reactions has been developed by using Weizmann 1 calculations, and 29 DFT methods and 6 ab initio wave-function theory (WFT) methods have been tested against the new database as well as against an older database for hydrogen atom transfer reactions. Among the tested hybrid DFT methods without kinetic energy density, MPW1K is the most accurate model for calculations of barrier heights. Among the tested hybrid meta DFT methods, BB1K and MPWB1K are the two most accurate models for the calculations of barrier heights. Overall, the results show that BB1K and MPWB1K are the two best DFT methods for calculating barrier heights, followed in order by MPW1K, MPWKCIS1K, B1B95, MPW1B95, BH and HLYP, B97-2, mPW1PW91, and B98. The popular B3LYP method has a mean unsigned error four times larger than that of BB1K. Of the methods tested, QCISD(T) is the best ab initio WFT method for barrier height calculations, and QCISD is second best, but QCISD is outperformed by the BB1K, MPWB1K, MPWKCIS1K, and MPW1K methods.