Theoretical Study of the Gas-Phase Reactions of NO_3 Radical with a Series of trans-2-Unsaturated Aldehydes: From Acrolein to trans-2- Octenal

摘要

The density functional theory with the BH&HLYP functional has been used in this work to clarify discrepancies found in the literature about the effect of the increasing carbon chain on the reactivity of trans-2-alkenals from acrolein (C_3) to trans-2-octenal (C_8) with nitrate radical. In this work, it was found that (i) the alkyl chain length of the unsaturated aldehydes has little or no influence on the NO_3 reaction rate coefficients (ii) the abstraction of the aldehydic hydrogen from the alkenal is always dominant (83% for trans-2-butanal to trans-2-octenal). The addition channel, which mainly concerns the β addition, has a small influence (17% of the total reaction for the whole series). These results are in good agreement with the experimental studies performed by Zhao et al. in 2011 and by Kerdouci et al. in 2012. All these findings will be useful to complete or improve structure-activity relationships developed to predict the reactivity of NO_3 radicals with organic compounds.