Improving B3LYP heats of formation with three‐dimensional molecular descriptors
Improving B3LYP heats of formation with three‐dimensional molecular descriptors
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DOI：
10.1002/jcc.24308
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发表时间：
2016-05
影响因子：
3
通讯作者：
Yuwei Zhou;Jianming Wu;Xin Xu
中科院分区：
文献类型：
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作者：
Yuwei Zhou;Jianming Wu;Xin Xu
在本工作中，我们提出了扩展B3LYP方法的X3D方法，通过使用三维(3D)分子描述符校正其在碳氢化合物生成热(HC)上的错误。受广泛使用的Wiener指数的启发，这些3D描述子是为了改进最初的B3LYP方法，以更好地描述原子-原子、原子-键和键-键相互作用。除了只有45个物种的训练集之外，X3D方法还针对不同的化学组进行了验证，显示出总体上接近化学的准确性。具体地说，X3D改进了B3LYP，对于(SET 1)21个正构烷烃至n-C32H66，其平均绝对误差从28.4降低到0.3千卡/摩尔，对于(SET 2)n-C7H16及其分支异构体，从19.3到0.6千卡/摩尔，对于(SET 3)36个多环饱和HCS，从29.5到1.6千卡/摩尔，对于(SET 4)41个C6H8异构体，从8.6到1.1千卡/摩尔，(SET 5)41个苯基化合物为20.3~0.6千卡/摩尔，(SET 6)66个自由基为8.1~1.3千卡/摩尔等，并与G4结果进行了比较。©2016 Wiley期刊，Inc.
In the present work, we propose the X3D method that extends the B3LYP method by correcting its errors on heats of formation of hydrocarbons (HCs) with three‐dimensional (3D) molecular descriptors. Inspired by the widely used Wiener index, these 3D descriptors are developed to improve over the original B3LYP method for a better description of atom‐atom, atom‐bond and bond‐bond interactions. On top of a training set of only 45 species, the X3D method is validated against various sets of different chemistry, displaying an overall near chemical accuracy. In particular, X3D improves over B3LYP, reducing its mean absolute errors from 28.4 to 0.3 kcal/mol for (Set 1) 21 n‐alkanes up to n‐C32H66, from 19.3 to 0.6 kcal/mol for (Set 2) n‐C7H16 and its branched isomers, from 29.5 to 1.6 kcal/mol for (Set 3) 36 polycyclic saturated HCs, from 8.6 to 1.1 kcal/mol for (Set 4) 41 C6H8 isomers of rings, alkenes, alkynes, and cumulenes, from 20.3 to 0.6 kcal/mol for (Set 5) 41 benzene‐based compounds, and 8.1 to 1.3 kcal/mol for (Set 6) 66 radicals, etc. Comparisons with the G4 results are also presented. © 2016 Wiley Periodicals, Inc.