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Accurate bond dissociation enthalpies by using doubly hybrid XYG3 functional
Author(s) -
Zhang Igor Ying,
Wu Jianming,
Luo Yi,
Xu Xin
Publication year - 2011
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.21764
Subject(s) - chemistry , dissociation (chemistry) , bond dissociation energy , standard enthalpy of formation , enthalpy , covalent bond , molecule , density functional theory , computational chemistry , standard enthalpy change of formation , thermodynamics , organic chemistry , physics
In this work, we examine the performance of XYG3, a newly developed doubly hybrid density functional (Zhang, Xu, and Goddard III, Proc Natl Acad Sci USA 2009, 106, 4963), to calculate covalent bond dissociation enthalpy (BDE). We use 5 atoms, 32 molecular radicals, and 116 closed‐shell molecules to set up 142 bond dissociation reactions. For the total of 148 heats of formation (HOFs) and 142 BDEs, XYG3 leads to mean absolute deviations (MADs) of 1.45 and 1.87 kcal/mol, respectively. In comparison with some other functionals, MADs for HOFs are 2.31 (M06‐2X), 2.98 (B2PLYP‐D), 3.04 (BMK), 3.96 (B3LYP), 4.47 (B2PLYP), 5.42 (B2GP‐PLYP), 6.46 (PBE0), and 29.93 kcal/mol (B3P86), and the corresponding errors for BDEs are 2.06 (M06‐2X), 2.25 (BMK), 2.51 (B2PLYP‐D), 2.89 (B2GP‐PLYP), 3.30 (B3P86), 3.44 (B2PLYP), 3.87 (PBE0), and 6.14 kcal/mol (B3LYP). © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011