A Theoretical Study of H-Abstractions of Benzaldehyde by H, O3(P), 3O2, OH, HO2, and CH3Radicals: Ab Initio Rate Coefficients and Their Uncertainty Quantification

Hao Zhao, Yingjia Zhang, Qian Zhao, Yang Li, Zuohua Huang

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Benzaldehyde is a vital intermediate during the oxidation of toluene and oxygenated aromatics, but benzaldehyde's combustion chemistry currently gains little attention. The H-atom abstraction of benzaldehyde is one critical reaction class, yet its rate coefficients rely on the analogy of molecular similarity. For this reason, we have employed the ab initio calculations at the CCSD(T)/cc-pVTZ//M06-2X/6-311+g(d,p) level of theory, along with the RRKM master equation to predict the rate coefficients of H-abstraction reactions of benzaldehyde by H, O3(P), 3O2, OH, HO2, and CH3radicals. The calculated rate coefficients of benzaldehyde + OH generally agree with literature measurements. From the branching ratio analysis, all the H-abstractions from ring sites can be neglected in kinetic model construction except by OH radical at temperature above 1700 K, where the ring sites contribute a relatively large branching ratio to consume benzaldehyde. A random sampling method has been used to estimate the global uncertainty in the calculated rate coefficients. The logarithm of uncertainty is proportional to the reciprocal temperature, and the global uncertainty is primarily derived from the energy errors and is almost independent of the attacking species. Comparison between benzaldehyde and acetaldehyde reveals that their rate coefficients are consistent only in H-abstractions by H and HO2but are conflictive in other reactions, especially in the case of OH. By incorporating the new calculations, existing models show a faster prediction in autoignition delay times of benzaldehyde. This study reports the first high-level ab initio calculations for the H-atom abstraction reaction class of benzaldehyde. It is necessary for the future comprehensive kinetic modeling of aromatic aldehyde.
Original languageEnglish (US)
Pages (from-to)7523-7533
Number of pages11
JournalJournal of Physical Chemistry A
Volume126
Issue number41
DOIs
StatePublished - Oct 20 2022
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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