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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

O–H Bond Dissociation Energies A

Bun Chan A B , Michael Morris A and Leo Radom A B

A School of Chemistry and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Sydney, NSW 2006, Australia.

B Corresponding authors. Email: chan_b@chem.usyd.edu.au; radom@chem.usyd.edu.au

Australian Journal of Chemistry 64(4) 394-402 http://dx.doi.org/10.1071/CH11028
Submitted: 7 January 2011  Accepted: 8 March 2011   Published: 18 April 2011

Abstract

High-level composite, ab initio and density functional theory (DFT) procedures have been employed to study O–H bond dissociation energies (BDEs), as well as radical stabilization energies (RSEs) in the oxygen-centred radicals that are formed in the dissociation of the O–H bonds. Benchmark values are provided by Wn results up to W3.2 and W4.x. We are able to recommend revised BDE values for FO–H (415.6 ± 3 kJ mol–1), MeC(O)O–H (459.8 ± 6 kJ mol–1) and CF3CH2O–H (461.9 ± 6 kJ mol–1) on the basis of high-level calculations. We find that Gn-type procedures are generally reliable and cost-effective, and that some contemporary functionals and double-hybrid DFT procedures also provide adequate O–H BDEs/RSEs. We note that the variations in the O–H BDEs are associated with variations in the stabilities of not only the radicals but also the closed-shell precursor molecules. Most substituents destabilize both species, with σ-electron-withdrawing groups having larger destabilizing effects, while π-electron acceptors are stabilizing. Although there is little correlation between the stabilizing/destabilizing effects of the substituents and the RSEs, we present some general patterns in the RSEs that emerge from the present study.

Graphical Abstract Image


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