{"title":"精确全维势能表面上HO + SO↔H + so2反应的理论动力学研究","authors":"Xiaoshan Huang, Jie Qin, Jianxun Zhang, Jun Li","doi":"10.1002/kin.21645","DOIUrl":null,"url":null,"abstract":"<p>The reaction HO + SO → H + SO<sub>2</sub> (R<sub>t</sub>) and its reverse (R<sub>-t</sub>) play an important role in environment and the combustion of sulfur-containing fuels. However, their kinetics is of high uncertainty as its reaction profile is complicated with multiple deep complexes and channels. In this work, the kinetics and mechanisms of R<sub>t</sub> and R<sub>-t</sub> are studied comprehensively based on a newly developed full-dimensional accurate potential energy surface (PES) with the aid of machine learning. This highly accurate PES is interfaced with the software Gaussian. Then reliable information, including the energy, structures, and vibrational frequencies of the stationary points, as well as the minimum energy path and variational analysis can be efficiently determined. The variational transition state theory (VTST) and Rice−Ramsperger−Kassel−Marcus (RRKM) theory are employed to obtain the rate coefficients of each elementary reaction. The temperature- and pressure-dependent rate coefficients of R<sub>t</sub> are derived by the RRKM-based master equation with hindered rotor and free rotor model considered. In addition, the effect of isotope substitution for the hydrogen is investigated on the reaction kinetics. Meanwhile, the quasi-classical trajectory (QCT) calculation is performed on the PES-2020 to obtain the temperature-dependent reaction kinetics.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2023-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical kinetics investigations of the reaction HO + SO ↔ H + SO2 on an accurate full-dimensional potential energy surface\",\"authors\":\"Xiaoshan Huang, Jie Qin, Jianxun Zhang, Jun Li\",\"doi\":\"10.1002/kin.21645\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The reaction HO + SO → H + SO<sub>2</sub> (R<sub>t</sub>) and its reverse (R<sub>-t</sub>) play an important role in environment and the combustion of sulfur-containing fuels. However, their kinetics is of high uncertainty as its reaction profile is complicated with multiple deep complexes and channels. In this work, the kinetics and mechanisms of R<sub>t</sub> and R<sub>-t</sub> are studied comprehensively based on a newly developed full-dimensional accurate potential energy surface (PES) with the aid of machine learning. This highly accurate PES is interfaced with the software Gaussian. Then reliable information, including the energy, structures, and vibrational frequencies of the stationary points, as well as the minimum energy path and variational analysis can be efficiently determined. The variational transition state theory (VTST) and Rice−Ramsperger−Kassel−Marcus (RRKM) theory are employed to obtain the rate coefficients of each elementary reaction. The temperature- and pressure-dependent rate coefficients of R<sub>t</sub> are derived by the RRKM-based master equation with hindered rotor and free rotor model considered. In addition, the effect of isotope substitution for the hydrogen is investigated on the reaction kinetics. Meanwhile, the quasi-classical trajectory (QCT) calculation is performed on the PES-2020 to obtain the temperature-dependent reaction kinetics.</p>\",\"PeriodicalId\":13894,\"journal\":{\"name\":\"International Journal of Chemical Kinetics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2023-04-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Chemical Kinetics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/kin.21645\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Chemical Kinetics","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/kin.21645","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
HO + SO→H + SO2 (Rt)及其逆反应(R-t)在环境和含硫燃料的燃烧中起着重要作用。然而,由于其反应谱复杂,有多个深层配合物和通道,其动力学具有很大的不确定性。本文基于新开发的全维精确势能面(PES),借助机器学习技术,对Rt和R-t的动力学和机理进行了全面研究。这种高精度的PES与高斯软件接口。然后,可以有效地确定平稳点的能量、结构、振动频率等可靠信息,以及最小能量路径和变分分析。采用变分跃迁态理论(VTST)和Rice - Ramsperger - Kassel - Marcus (RRKM)理论计算了各基本反应的速率系数。在考虑阻碍转子和自由转子模型的情况下,利用基于rrkm的主方程推导了Rt的温度和压力相关速率系数。此外,还研究了同位素取代氢对反应动力学的影响。同时,对PES-2020进行了准经典轨迹(QCT)计算,获得了温度依赖性反应动力学。
Theoretical kinetics investigations of the reaction HO + SO ↔ H + SO2 on an accurate full-dimensional potential energy surface
The reaction HO + SO → H + SO2 (Rt) and its reverse (R-t) play an important role in environment and the combustion of sulfur-containing fuels. However, their kinetics is of high uncertainty as its reaction profile is complicated with multiple deep complexes and channels. In this work, the kinetics and mechanisms of Rt and R-t are studied comprehensively based on a newly developed full-dimensional accurate potential energy surface (PES) with the aid of machine learning. This highly accurate PES is interfaced with the software Gaussian. Then reliable information, including the energy, structures, and vibrational frequencies of the stationary points, as well as the minimum energy path and variational analysis can be efficiently determined. The variational transition state theory (VTST) and Rice−Ramsperger−Kassel−Marcus (RRKM) theory are employed to obtain the rate coefficients of each elementary reaction. The temperature- and pressure-dependent rate coefficients of Rt are derived by the RRKM-based master equation with hindered rotor and free rotor model considered. In addition, the effect of isotope substitution for the hydrogen is investigated on the reaction kinetics. Meanwhile, the quasi-classical trajectory (QCT) calculation is performed on the PES-2020 to obtain the temperature-dependent reaction kinetics.
期刊介绍:
As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.