OCS + OH 反应的气相和水介导机制

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2025-01-21 DOI:10.1039/D4CP04549A
Joel Leitão Nascimento and Tiago Vinicius Alves
{"title":"OCS + OH 反应的气相和水介导机制","authors":"Joel Leitão Nascimento and Tiago Vinicius Alves","doi":"10.1039/D4CP04549A","DOIUrl":null,"url":null,"abstract":"<p >We report a computational study of the gas-phase and water-mediated mechanisms for the oxidation of carbonyl sulfide (OCS) by the hydroxyl radical. To achieve reliable results, we employ a dual-level strategy within interpolated single-point energies (VTST-ISPE) at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. In the gas-phase mechanism, we have determined the rate constants by kinetic Monte Carlo simulation in the interval of temperatures of 250–550 K. The calculated rate constant, at room temperature, is 4.86 × 10<small><sup>−16</sup></small> cm<small><sup>3</sup></small> molecule<small><sup>−1</sup></small> s<small><sup>−1</sup></small>, in agreement with experimental measurement: 6.00 ± 4.00 × 10<small><sup>−16</sup></small> cm<small><sup>3</sup></small> molecule<small><sup>−1</sup></small> s<small><sup>−1</sup></small> [M. T. Leu and R. H. Smith, <em>J. Phys. Chem.</em>, 1981, <strong>85</strong>, 2570–2575]. The water-mediated mechanism, a more complex process than the gas-phase, revealed six reaction pathways. The application of the pre-equilibrium model allowed us to determine termolecular thermal rate constants. Considering the concentrations of water as a function of the relative humidity at 0 km altitude, we estimated effective rate constants. The magnitude of the rate coefficients for this mechanism suggested a negligible effect of the water in the OCS + OH reaction.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 7","pages":" 3748-3754"},"PeriodicalIF":2.9000,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Gas-phase and water-mediated mechanisms for the OCS + OH reaction†\",\"authors\":\"Joel Leitão Nascimento and Tiago Vinicius Alves\",\"doi\":\"10.1039/D4CP04549A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report a computational study of the gas-phase and water-mediated mechanisms for the oxidation of carbonyl sulfide (OCS) by the hydroxyl radical. To achieve reliable results, we employ a dual-level strategy within interpolated single-point energies (VTST-ISPE) at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. In the gas-phase mechanism, we have determined the rate constants by kinetic Monte Carlo simulation in the interval of temperatures of 250–550 K. The calculated rate constant, at room temperature, is 4.86 × 10<small><sup>−16</sup></small> cm<small><sup>3</sup></small> molecule<small><sup>−1</sup></small> s<small><sup>−1</sup></small>, in agreement with experimental measurement: 6.00 ± 4.00 × 10<small><sup>−16</sup></small> cm<small><sup>3</sup></small> molecule<small><sup>−1</sup></small> s<small><sup>−1</sup></small> [M. T. Leu and R. H. Smith, <em>J. Phys. Chem.</em>, 1981, <strong>85</strong>, 2570–2575]. The water-mediated mechanism, a more complex process than the gas-phase, revealed six reaction pathways. The application of the pre-equilibrium model allowed us to determine termolecular thermal rate constants. Considering the concentrations of water as a function of the relative humidity at 0 km altitude, we estimated effective rate constants. The magnitude of the rate coefficients for this mechanism suggested a negligible effect of the water in the OCS + OH reaction.</p>\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":\" 7\",\"pages\":\" 3748-3754\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-01-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d4cp04549a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d4cp04549a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

摘要

我们报告了羰基硫醚(OCS)被羟基自由基氧化的气相和水介导机制的计算研究。为了获得可靠的结果,我们在理论的CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ能级采用了双能级策略。在气相机理中,我们用动力学蒙特卡罗模拟确定了250 ~ 550 K温度区间内的速率常数。在室温下,计算得到的速率常数为4.86 × 10−16 cm3分子−1 s−1,与实验测量值6.00±4.00 × 10−16 cm3分子−1 s−1 [M]一致。T. Leu和R. H. Smith, J.物理学。化学。[j].农业工程学报,1998,25(2):444 - 444。水介导的反应机制比气相反应更为复杂,揭示了六种反应途径。预平衡模型的应用使我们能够确定三分子热速率常数。考虑到水的浓度是0 km高度相对湿度的函数,我们估计了有效速率常数。该反应速率系数的大小表明,水对OCS + OH反应的影响可以忽略不计。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

摘要图片

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
Gas-phase and water-mediated mechanisms for the OCS + OH reaction†

We report a computational study of the gas-phase and water-mediated mechanisms for the oxidation of carbonyl sulfide (OCS) by the hydroxyl radical. To achieve reliable results, we employ a dual-level strategy within interpolated single-point energies (VTST-ISPE) at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. In the gas-phase mechanism, we have determined the rate constants by kinetic Monte Carlo simulation in the interval of temperatures of 250–550 K. The calculated rate constant, at room temperature, is 4.86 × 10−16 cm3 molecule−1 s−1, in agreement with experimental measurement: 6.00 ± 4.00 × 10−16 cm3 molecule−1 s−1 [M. T. Leu and R. H. Smith, J. Phys. Chem., 1981, 85, 2570–2575]. The water-mediated mechanism, a more complex process than the gas-phase, revealed six reaction pathways. The application of the pre-equilibrium model allowed us to determine termolecular thermal rate constants. Considering the concentrations of water as a function of the relative humidity at 0 km altitude, we estimated effective rate constants. The magnitude of the rate coefficients for this mechanism suggested a negligible effect of the water in the OCS + OH reaction.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
相关文献
二甲双胍通过HDAC6和FoxO3a转录调控肌肉生长抑制素诱导肌肉萎缩
IF 8.9 1区 医学Journal of Cachexia, Sarcopenia and MusclePub Date : 2021-11-02 DOI: 10.1002/jcsm.12833
Min Ju Kang, Ji Wook Moon, Jung Ok Lee, Ji Hae Kim, Eun Jeong Jung, Su Jin Kim, Joo Yeon Oh, Sang Woo Wu, Pu Reum Lee, Sun Hwa Park, Hyeon Soo Kim
具有疾病敏感单倍型的非亲属供体脐带血移植后的1型糖尿病
IF 3.2 3区 医学Journal of Diabetes InvestigationPub Date : 2022-11-02 DOI: 10.1111/jdi.13939
Kensuke Matsumoto, Taisuke Matsuyama, Ritsu Sumiyoshi, Matsuo Takuji, Tadashi Yamamoto, Ryosuke Shirasaki, Haruko Tashiro
封面:蛋白质组学分析确定IRSp53和fastin是PRV输出和直接细胞-细胞传播的关键
IF 3.4 4区 生物学ProteomicsPub Date : 2019-12-02 DOI: 10.1002/pmic.201970201
Fei-Long Yu, Huan Miao, Jinjin Xia, Fan Jia, Huadong Wang, Fuqiang Xu, Lin Guo
来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
期刊最新文献
Tailoring OER/ORR Activity in TM1N4 Catalysts through First-/Second-Shell Nitrogen Doping: A Density Functional Theory Investigation The influence of fluorine spin-diffusion on 13C solid-state NMR line shapes of CF3 groups Biphenylene Concentric Nanorings as High-Performance Anode Materials for Lithium-Ion Batteries: A DFT-Based Study on Lithium Intercalation and Capacity Enhancement Insight into the interface properties of γ-TiAl/α2-Ti3Al with La doping obtained by first-principles calculations On pH controlling of the reaction mechanism: Interactions of Au(I)-NHC Complex with Thioredoxin Reductase (modeled by Cysteine and Selenocysteine); ab initio and DFT calculations.
×
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
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 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 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1