Theoretical study on the gas-phase reaction of acetaldehyde with methoxy radical

Abstract

The reaction of acetaldehyde with methoxy radical has been investigated theoretically by means of quantum chemistry methods at the BMC-QCISD//B3LYP/6-311+G(d,p) level. The title reaction included three manners, namely, H-abstraction, C-addition-elimination, and C-addition-isomerization-elimination. Based on our calculated results, the formation of adduct IM1 is not a nucleophilic addition reaction, but a π addition reaction. Rice–Ramsperger–Kassel–Marcus-transition state theory calculations are carried out for the total and individual rate constants of the determinant channels over a wide range of temperatures and pressures. The major products for the title reaction are CH3CO and CH3OH. The calculated rate constant (8.73 × 10−15 cm3 molecule−1 s−1) agrees well with the experimental value (k1 = 8.30 × 10−15 cm3 molecule−1 s−1 and 4.23 × 10−15 cm3 molecule−1 s−1).

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Funding

This work was supported by the Natural Science Foundations of China (No. 21707062), Scientific Research Starting Foundation of Mianyang Normal University (No. QD2016A007), and Sichuan Education Department Fund (No. 17ZB0207).

This work was also supported by Sichuan Education Department Fund (No. 12ZA080) and Mianyang Normal University for Excellent Plan Fund (No. QD2012A06) and supported by the Open Project Program of Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), Beijing 100048, China.

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Correspondence to Yunju Zhang.

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Zhang, Y., Song, R., Sun, Y. et al. Theoretical study on the gas-phase reaction of acetaldehyde with methoxy radical. Struct Chem 30, 127–135 (2019). https://doi.org/10.1007/s11224-018-1181-6

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Keywords

  • Acetaldehyde
  • Methoxy radical
  • PES
  • RRKM