An improved B3LYP method in the calculation of organic thermochemistry and reactivity
An improved B3LYP method in the calculation of organic thermochemistry and reactivity
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有机热化学和反应活性计算中改进的B3LYP方法
DOI：
10.1016/j.comptc.2013.04.009
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发表时间：
2013-07-01
影响因子：
2.8
通讯作者：
Wang, Baoshan
中科院分区：
文献类型：
--
作者：
Lu, Lilin;Hu, Hui;Wang, Baoshan
B3LYP混合密度泛函已经使用了几十年，但它的三个经验参数直接从B3PW91泛函复制。我们发现，这些任意的参数导致了B3LYP对有机大分子形成的描述的严重缺陷和B3LYP对有机化学反应性的定性失败。使用严格优化的经验参数，即a（0）= 0.20，a（x）= 0.67，a（c）= 0.84，B3LYP确实明显优于旧公式，具有与最先进的密度泛函相当甚至更好的性能。结果表明，采用优化后的半经验参数的B3LYP方法在化学中，特别是在有机大分子的热化学和反应性的计算中，仍有很好的应用前景.皇冠版权所有（C）2013由爱思唯尔B.V.出版保留所有权利。
The B3LYP hybrid density functional has been used for decades but its three empirical parameters were copied straightforwardly from the B3PW91 functional. We found that the serious flaw of B3LYP for the enthalpies of formation of large organic molecules and the qualitative failure of B3LYP for organic chemical reactivity are caused by these arbitrary parameters. Using the rigorously optimized empirical parameters, namely, a(0) = 0.20, a(x) = 0.67, and a(c) = 0.84, B3LYP does outperform the old formula significantly with the comparable or even better performance than the state-of-the-art density functionals. It is suggested that the B3LYP method with the optimized semiempirical parameters might continue to be a good density functional in chemistry especially in the calculations of thermochemistry and reactivity of large organic molecules. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.