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Evaluation of density functional theory in the bond rupture of octane
Author(s) -
Goldstein E.,
Haught M.,
Tang Y.
Publication year - 1998
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/(sici)1096-987x(19980130)19:2<154::aid-jcc8>3.0.co;2-t
Subject(s) - additive function , chemistry , octane , density functional theory , radical , computational chemistry , thermodynamics , organic chemistry , physics , mathematics , mathematical analysis
Density functional methods at the 6‐31G* level are applied to the rupture of n ‐octane into methyl–heptyl, ethyl–hexyl, propyl–pentyl, and butyl–butyl radical fragments. The energetics of the radicals at UMP3, UMP2/6‐31G*//UHF/6‐31G* (hereafter referred to as UMP), are compared to UB3LYP/6‐31G* results (referred to as UB). Although the UMP approach matches additivity energies to within 5 kcal/mol, it fails to mimic the overall energetic trend. The UB energies agree with additivity estimates and trends to within 1–2 kcal/mol and radical entropies deviate by only 2 e.u. from available experimental data. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 154–167, 1998