American Chemical Society
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Trends in Bond Dissociation Energies of Alcohols and Aldehydes Computed with Multireference Averaged Coupled-Pair Functional Theory

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journal contribution
posted on 2014-05-01, 00:00 authored by Victor B. Oyeyemi, John A. Keith, Emily A. Carter
As part of our ongoing investigation of the combustion chemistry of oxygenated molecules using multireference correlated wave function methods, we report bond dissociation energies (BDEs) in C1–C4 alcohols (from methanol to the four isomers of butanol) and C1–C4 aldehydes (from methanal to butanal). The BDEs are calculated with a multireference averaged coupled-pair functional-based scheme. We compare these multireference BDEs with those derived from experiment and single-reference methods. Trends in BDEs for the alcohols and aldehydes are rationalized by considering geometry relaxations of dissociated radical fragments, resonance stabilization, and hyperconjugation. Lastly, we discuss the conjectured association between bond strengths and rates of hydrogen abstraction by hydroxyl radicals. In general, abstraction reaction rates are higher at sites where the C–H bond energies are lower (and vice versa). However, comparison with available rate data shows this inverse relationship between bond strengths and abstraction rates does not hold at all temperatures.