{"title":"HCNO + C6H5反应的理论研究:机理和动力学。","authors":"Trong Nghia Nguyen, Hue Minh Thi Nguyen","doi":"10.1007/s00894-025-06456-y","DOIUrl":null,"url":null,"abstract":"<div><h3>Context</h3><p>The reaction between HCNO and C<sub>6</sub>H<sub>5</sub> is of relevance in environments such as combustion and atmospheric chemistry, where both species are known to coexist. In this study, we report the reaction mechanism and kinetics of their gas-phase reaction. The reaction proceeds via the addition of C<sub>6</sub>H<sub>5</sub> to the carbon atom of HCNO, forming a pre-reaction complex (COMP) and a low-lying transition state (T0/1) that leads to a key intermediate (IS1). IS1 decomposes into C<sub>6</sub>H<sub>5</sub>CH + NO (PR2), C<sub>6</sub>H<sub>5</sub>CNO + H (PR3), and HCN + C<sub>6</sub>H<sub>5</sub>O (PR4). Minor pathways include hydrogen abstraction forming C<sub>6</sub>H<sub>6</sub> + CNO (PR1) and oxygen-site addition yielding IS2, which also leads to HCN + C<sub>6</sub>H<sub>5</sub>O (PR5). Kinetic results indicate that IS1 dominates below 1500 K at 760 Torr. At higher temperatures, PR2 (39.5–54.3%) and PR3 (6.5–35.0%) become the main channels, with a notable contribution from PR1 (6.5–19.4%) and minor yields from PR4 (< 3.0%) and PR5 (< 2.5%) over the entire temperature range at this pressure.</p><h3>Methods</h3><p>All structures were calculated at the ROCBS-QB3, ROCCSD(T)//B3LYP, and UCCSD(T)//B3LYP levels of theory. Rate constants were evaluated using TST and RRKM/master equation methods with Eckart tunneling corrections over the 300–2500 K and 100–7600 Torr ranges.</p></div>","PeriodicalId":651,"journal":{"name":"Journal of Molecular Modeling","volume":"31 8","pages":""},"PeriodicalIF":2.5000,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical Study on the HCNO + C6H5 Reaction: Mechanism and Kinetics\",\"authors\":\"Trong Nghia Nguyen, Hue Minh Thi Nguyen\",\"doi\":\"10.1007/s00894-025-06456-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><h3>Context</h3><p>The reaction between HCNO and C<sub>6</sub>H<sub>5</sub> is of relevance in environments such as combustion and atmospheric chemistry, where both species are known to coexist. In this study, we report the reaction mechanism and kinetics of their gas-phase reaction. The reaction proceeds via the addition of C<sub>6</sub>H<sub>5</sub> to the carbon atom of HCNO, forming a pre-reaction complex (COMP) and a low-lying transition state (T0/1) that leads to a key intermediate (IS1). IS1 decomposes into C<sub>6</sub>H<sub>5</sub>CH + NO (PR2), C<sub>6</sub>H<sub>5</sub>CNO + H (PR3), and HCN + C<sub>6</sub>H<sub>5</sub>O (PR4). Minor pathways include hydrogen abstraction forming C<sub>6</sub>H<sub>6</sub> + CNO (PR1) and oxygen-site addition yielding IS2, which also leads to HCN + C<sub>6</sub>H<sub>5</sub>O (PR5). Kinetic results indicate that IS1 dominates below 1500 K at 760 Torr. At higher temperatures, PR2 (39.5–54.3%) and PR3 (6.5–35.0%) become the main channels, with a notable contribution from PR1 (6.5–19.4%) and minor yields from PR4 (< 3.0%) and PR5 (< 2.5%) over the entire temperature range at this pressure.</p><h3>Methods</h3><p>All structures were calculated at the ROCBS-QB3, ROCCSD(T)//B3LYP, and UCCSD(T)//B3LYP levels of theory. Rate constants were evaluated using TST and RRKM/master equation methods with Eckart tunneling corrections over the 300–2500 K and 100–7600 Torr ranges.</p></div>\",\"PeriodicalId\":651,\"journal\":{\"name\":\"Journal of Molecular Modeling\",\"volume\":\"31 8\",\"pages\":\"\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2025-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Modeling\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00894-025-06456-y\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"BIOCHEMISTRY & MOLECULAR BIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Modeling","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s00894-025-06456-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
引用次数: 0
摘要
背景:HCNO和C6H5之间的反应在燃烧和大气化学等环境中具有相关性,已知这两种物质共存。在本研究中,我们报道了它们的气相反应机理和动力学。反应通过将C6H5添加到HCNO的碳原子上,形成反应前配合物(COMP)和低洼过渡态(T0/1),形成关键中间体(IS1)。IS1分解为C6H5CH + NO (PR2)、C6H5CNO + H (PR3)和HCN + C6H5O (PR4)。次要途径包括抽氢生成C6H6 + CNO (PR1)和氧位点加成生成IS2,后者也生成HCN + C6H5O (PR5)。动力学结果表明,在1500 K和760 Torr下,IS1占主导地位。在较高温度下,PR2(39.5-54.3%)和PR3(6.5-35.0%)成为主要通道,PR1的贡献显著(6.5-19.4%),PR4的产率较小(方法:所有结构均在ROCBS-QB3、ROCCSD(T)//B3LYP和UCCSD(T)//B3LYP理论水平上进行计算。在300-2500 K和100-7600 Torr范围内,使用TST和RRKM/主方程方法计算速率常数,并采用Eckart隧道修正。
Theoretical Study on the HCNO + C6H5 Reaction: Mechanism and Kinetics
Context
The reaction between HCNO and C6H5 is of relevance in environments such as combustion and atmospheric chemistry, where both species are known to coexist. In this study, we report the reaction mechanism and kinetics of their gas-phase reaction. The reaction proceeds via the addition of C6H5 to the carbon atom of HCNO, forming a pre-reaction complex (COMP) and a low-lying transition state (T0/1) that leads to a key intermediate (IS1). IS1 decomposes into C6H5CH + NO (PR2), C6H5CNO + H (PR3), and HCN + C6H5O (PR4). Minor pathways include hydrogen abstraction forming C6H6 + CNO (PR1) and oxygen-site addition yielding IS2, which also leads to HCN + C6H5O (PR5). Kinetic results indicate that IS1 dominates below 1500 K at 760 Torr. At higher temperatures, PR2 (39.5–54.3%) and PR3 (6.5–35.0%) become the main channels, with a notable contribution from PR1 (6.5–19.4%) and minor yields from PR4 (< 3.0%) and PR5 (< 2.5%) over the entire temperature range at this pressure.
Methods
All structures were calculated at the ROCBS-QB3, ROCCSD(T)//B3LYP, and UCCSD(T)//B3LYP levels of theory. Rate constants were evaluated using TST and RRKM/master equation methods with Eckart tunneling corrections over the 300–2500 K and 100–7600 Torr ranges.
期刊介绍:
The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling.
Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry.
Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.