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Improving B 3 LYP heats of formation with three‐dimensional molecular descriptors
Author(s) -
Zhou Yuwei,
Wu Jianming,
Xu Xin
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24308
Subject(s) - chemistry , benzene , x3d , atom (system on chip) , structural isomer , computational chemistry , stereochemistry , organic chemistry , computer science , vrml , embedded system , the internet , world wide web
In the present work, we propose the X 3D 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 X 3D method is validated against various sets of different chemistry, displaying an overall near chemical accuracy. In particular, X 3D 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 ‐C 32 H 66 , from 19.3 to 0.6 kcal/mol for (Set 2) n ‐C 7 H 16 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 C 6 H 8 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.