Issue 7, 2023

Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Abstract

The addition mechanism of the OH-initiated oxidation of allyl methyl sulfide (AMS) under atmospheric conditions was studied theoretically using both density functional theory (DFT) and the SVECV-f12 composite method. We found that the addition does not occur directly but rather through a pre-reactive complex that serves as a previous stage for addition at both the C1 and C2 positions. However, based on thermodynamics the addition at C2 possibly occurs by branching of the C1 addition mechanism. Once the addition proceeds, the reaction with O2 under atmospheric conditions produces RO2 radicals that can decompose in multiple ways. Complex mechanisms of intramolecular rearrangement and decomposition both in the absence and presence of NOx have been examined. The thermodynamically most favourable decomposition paths produce 2-hydroxy-acetaldehyde, 2-methyl-thio-acetaldehyde, formaldehyde, and the methyl thiomethyl peroxy (MSP) intermediate. This latter species is proposed as the main source of sulfur dioxide (SO2), which is the product found in the highest yield during the experimental determinations.

Graphical abstract: Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Supplementary files

Article information

Article type
Paper
Submitted
16 Qun 2023
Accepted
03 Cax 2023
First published
05 Cax 2023
This article is Open Access
Creative Commons BY-NC license

Environ. Sci.: Atmos., 2023,3, 1075-1089

Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

A. L. Cardona, M. B. Blanco, M. A. Teruel and O. N. Ventura, Environ. Sci.: Atmos., 2023, 3, 1075 DOI: 10.1039/D3EA00010A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements