Bond dissociation energies and radical stabilization energies: An assessment of contemporary theoretical procedures

Ambili S. Menon, Geoffrey P F Wood, Damian Moran, Leo Radom*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

87 Citations (Scopus)

Abstract

Various contemporary theoretical procedures have been tested for their accuracy in predicting the bond dissociation energies (BDEs) and the radical stabilization energies (RSEs) for a test set of 22 monosubstituted methyl radicals. The procedures considered include the high-level W1', Wl', CBS-QB3, ROCBS-QB3, G3-(MP2)-RAD, and G3X(MP2)-RAD methods, unrestricted and restricted versions of the double-hybrid density functional theory (DFT) procedures B2-PLYP and MPW2-PLYP, and unrestricted and restricted versions of the hybrid DFT procedures BMK and MPWB1K, as well as the unrestricted DFT procedures UM05 and UM05-2X. The high-level composite procedures show very good agreement with experiment and are used to evaluate the performance of the comparatively less expensive DFT procedures. RMPWB1K and both RBMK and UBMK give very promising results for absolute BDEs, while additionally restricted and unrestricted X2-PLYP methods and UM05-2X give excellent RSE values. UM05, UB2-PLYP, UMPW2-PLYP, UM05-2X, and UMPWB1K are among the less well performing methods for BDEs, while UMPWB1K and UM05 perform less well for RSEs. The high-level theoretical results are used to recommend alternative experimental BDEs for propyne, acetaldehyde, and acetic acid.

Original languageEnglish
Pages (from-to)13638-13644
Number of pages7
JournalJournal of Physical Chemistry A
Volume111
Issue number51
DOIs
Publication statusPublished - 27 Dec 2007
Externally publishedYes

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