DFT研究了DMS + O3反应的机理和动力学

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Shuangjun Wang, Hui Zhao, Dong Chen, Chenggang Lu, Yizhen Tang
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引用次数: 0

摘要

在CCSD(T)/6-311++G(3df,2pd)//M06-2X/6-311++G(d,p)理论水平下,计算了臭氧与二甲基硫化物(DMS)反应的势能面(PES)。结果表明,在单重态PES上,加消机制占主导地位,h -抽象机制竞争较小。主要通道从臭氧和DMS的加入开始,导致弱中间IM1,随后通过约38.8 kJ/mol的屏障分解为DMSO和1O2。当势垒为64.0 kJ/mol时,HO3 + CH3SCH2的形成是次要的。此外,DMSO + 1O2还可发生进一步反应,生成多种产物。取代机制定位在三态聚醚上,但势垒较高,可以忽略不计。在200 ~ 1000 K范围内计算了DMSO + 1O2和HO3 + CH3SCH2两个通道的速率常数。在298 K和1atm下,总速率常数为1.13 × 10-20 cm3·分子-1·s-1,与前人实验数据吻合较好。在整个温度范围内,总速率常数与温度呈正相关。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

DFT investigations on the mechanisms and kinetics for the DMS + O3 reaction

DFT investigations on the mechanisms and kinetics for the DMS + O3 reaction

The potential energy surface (PES) for the reaction of ozone with dimethyl sulfide (DMS) was calculated at the CCSD(T)/6-311++G(3df,2pd)//M06-2X/6-311++G(d,p) levels of theory. Result shows that on the singlet PES the addition–elimination mechanism is dominant, and H-abstraction mechanism is less competitive. The major channel starts from the addition of ozone and DMS leading to a weak intermediate IM1, which decomposes subsequently to DMSO and 1O2 via a barrier around 38.8 kJ/mol. With a barrier of 64.0 kJ/mol, the formation of HO3 + CH3SCH2 via H-abstraction mechanism is subdominant. Besides, DMSO + 1O2 can take place further reactions to produce several products. The substitution mechanism was located on the triplet PES, however, with a rather high barrier it is negligible. Furthermore, the rate constants for the two channels leading to DMSO + 1O2 and HO3 + CH3SCH2 were calculated from 200 to 1000 K. The total rate constant is 1.13 × 10-20 cm3·molecule-1·s-1 at 298 K and 1 atm, in good agreement with previous experimental data. The overall rate constants are positive temperature dependent in the whole temperature range.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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