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Evaluation of density functional theory in the bond rupture of octane

✍ Scribed by Goldstein, E.; Haught, M.; Tang, Y.

Publisher: John Wiley and Sons
Year: 1998
Tongue: English
Weight: 257 KB
Volume: 19
Category: Article
ISSN: 0192-8651
DOI: 10.1002/(sici)1096-987x(19980130)19:2<154::aid-jcc8>3.0.co;2-t

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✦ Synopsis

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, UMP2r6-Ž . 31G*rrUHFr6-31G* hereafter referred to as UMP , are compared to Ž . UB3LYPr6-31G* results referred to as UB . Although the UMP approach matches additivity energies to within 5 kcalrmol, it fails to mimic the overall energetic trend. The UB energies agree with additivity estimates and trends to within 1᎐2 kcalrmol and radical entropies deviate by only 2 e.u. from available experimental data.

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