Computational Insights into the Formation of Methyl Formate and Glycolaldehyde via Amorphous ISM Ice

IF 2.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Mateus Augusto Martins de Paiva, Breno Rodrigues Lamaghere Galvão and Heitor Avelino De Abreu*, 
{"title":"Computational Insights into the Formation of Methyl Formate and Glycolaldehyde via Amorphous ISM Ice","authors":"Mateus Augusto Martins de Paiva,&nbsp;Breno Rodrigues Lamaghere Galvão and Heitor Avelino De Abreu*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0019010.1021/acsearthspacechem.4c00190","DOIUrl":null,"url":null,"abstract":"<p >In the realm of Complex Organic Molecules (COMs) detected within the Interstellar Medium (ISM), glycolaldehyde stands out as a pivotal player due to its dual significance as the simplest sugar and a precursor of life-sustaining molecules such as ribose. Coexisting in substantial concentrations with glycolaldehyde is its isomer, methyl formate, raising questions about a potential shared formation pathway. Recent research hints at the essential role of amorphous water ice in COM formation within dense ISM nebulae. This study revisits a promising two-step pathway for glycolaldehyde synthesis, initiated by the reaction of formaldehyde with the formyl radical, followed by hydrogenation of the resulting intermediate. In addition to employing a more rigorous level of calculation, the Langmuir–Hinshelwood mechanism is explored, while also predicting the possibility of methyl formate formation from the same starting materials. Simulation efforts, using water clusters comprising 18 and 25 molecules, leverage both Density Functional Theory (DFT) and Coupled Cluster (CC) methods at distinct sites of the surface. The findings reveal that, at the DFT level, the proposed reaction leads to glycolaldehyde formation with no energy barriers, exhibiting a significant relative energy reduction of up to 129% relative to the gas-phase reaction. Conversely, at the CC level, a modest 19 kJ mol<sup>–1</sup> barrier is encountered at 10 K, representing a 45% reduction. We show that formation of methyl formate via this pathway is not feasible, with higher energy barriers than the primary glycolaldehyde production. Analysis of the adsorption energies suggests distinct behaviors, with glycolaldehyde intermediates remaining adsorbed until the formation of the final molecule, while methyl formate exhibits sufficient energy for desorption before the final hydrogenation step.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2442–2451 2442–2451"},"PeriodicalIF":2.9000,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00190","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Earth and Space Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsearthspacechem.4c00190","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

In the realm of Complex Organic Molecules (COMs) detected within the Interstellar Medium (ISM), glycolaldehyde stands out as a pivotal player due to its dual significance as the simplest sugar and a precursor of life-sustaining molecules such as ribose. Coexisting in substantial concentrations with glycolaldehyde is its isomer, methyl formate, raising questions about a potential shared formation pathway. Recent research hints at the essential role of amorphous water ice in COM formation within dense ISM nebulae. This study revisits a promising two-step pathway for glycolaldehyde synthesis, initiated by the reaction of formaldehyde with the formyl radical, followed by hydrogenation of the resulting intermediate. In addition to employing a more rigorous level of calculation, the Langmuir–Hinshelwood mechanism is explored, while also predicting the possibility of methyl formate formation from the same starting materials. Simulation efforts, using water clusters comprising 18 and 25 molecules, leverage both Density Functional Theory (DFT) and Coupled Cluster (CC) methods at distinct sites of the surface. The findings reveal that, at the DFT level, the proposed reaction leads to glycolaldehyde formation with no energy barriers, exhibiting a significant relative energy reduction of up to 129% relative to the gas-phase reaction. Conversely, at the CC level, a modest 19 kJ mol–1 barrier is encountered at 10 K, representing a 45% reduction. We show that formation of methyl formate via this pathway is not feasible, with higher energy barriers than the primary glycolaldehyde production. Analysis of the adsorption energies suggests distinct behaviors, with glycolaldehyde intermediates remaining adsorbed until the formation of the final molecule, while methyl formate exhibits sufficient energy for desorption before the final hydrogenation step.

通过无定形ISM冰形成甲酸甲酯和乙醇醛的计算见解
在星际介质(ISM)中检测到的复杂有机分子(COMs)领域中,乙醇醛作为关键参与者脱颖而出,因为它具有双重意义,既是最简单的糖,又是维持生命的分子(如核糖)的前体。与乙醇醛大量共存的是它的异构体,甲酸甲酯,这就提出了一个潜在的共享形成途径的问题。最近的研究暗示了致密ISM星云中非晶水冰在COM形成中的重要作用。本研究回顾了一个有希望的两步乙醇醛合成途径,由甲醛与甲酰自由基的反应引发,然后是产生的中间体的氢化。除了采用更严格的计算水平外,还探索了Langmuir-Hinshelwood机制,同时还预测了从相同的起始材料生成甲酸甲酯的可能性。模拟工作使用了由18和25个分子组成的水团簇,在表面的不同位置利用密度泛函理论(DFT)和耦合团簇(CC)方法。研究结果表明,在DFT水平上,所提出的反应导致了乙醇醛的形成,没有能量障碍,相对于气相反应显示出高达129%的相对能量降低。相反,在CC水平上,在10 K时遇到一个19 kJ的mol-1势垒,代表45%的减少。我们表明,通过这种途径形成甲酸甲酯是不可行的,具有比初级乙醇醛生产更高的能量势垒。对吸附能的分析表明了不同的行为,乙醇醛中间体在最终分子形成之前仍然被吸附,而甲酸甲酯在最终加氢步骤之前表现出足够的能量来解吸。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
ACS Earth and Space Chemistry
ACS Earth and Space Chemistry Earth and Planetary Sciences-Geochemistry and Petrology
CiteScore
5.30
自引率
11.80%
发文量
249
期刊介绍: The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信