第一代反式-2-己烯醛臭氧分解产物：机理的新探讨

IF 2.7 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2025-04-02 DOI:10.1021/acs.jpca.4c0760810.1021/acs.jpca.4c07608

Najoua Derbel*, Alexander Alijah, Struan H. Robertson, Thomas Lauvaux and Lilian Joly,

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引用次数: 0

摘要

以M06-2X /AVTZ预优化核构型获得的高精度CCSD(T)-F12b/AVTZ能值为基础，对反式2-己烯醛臭氧分解反应进行了理论研究。利用主方程求解器MESMER建立了动力学模型。除了预期的稳定氧化产物1-丁醛（17%）和乙二醛（35%）外，乙二醛通道上形成二次臭氧，这是主要的第一代产物（49%）。进一步表明，乙二醛是通过两种相互竞争的途径产生的，其中一种途径导致同时产生甲酸丙酯（18%）。所有这些机制的纳入解释了实验结果，并首次确定了实验碳赤字的起源。

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First-Generation Products of Trans-2-Hexenal Ozonolyis: A New Look at the Mechanism

The ozonolysis reaction of trans-2-hexenal was studied theoretically on the basis of highly accurate CCSD(T)-F12b/AVTZ energy values obtained in M06–2X/AVTZ preoptimized nuclear configurations. The kinetics was modeled with the help of the master equation solver MESMER. Apart from the expected stable oxidation products 1-butanal (17%) and glyoxal (35%), a secondary ozonide is formed on the glyoxal channel, which is the principal first-generation product (49%). It is further shown that glyoxal is created on two competing pathways, one of which leads to simultaneous production of the ester propylformate (18%). The inclusion of all of these mechanisms explains the experimental findings and identifies for the first time the origin of the experimental carbon deficit.

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来源期刊

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

期刊介绍： The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.