Lijie Liu, Hao Wu, Yanlin Fu, Xiaoxiao Lu, Xingan Wang, Dong H Zhang, Bina Fu
{"title":"OH漫游是反ch3choo + H2O反应生成CH3COOH和H2O的关键途径。","authors":"Lijie Liu, Hao Wu, Yanlin Fu, Xiaoxiao Lu, Xingan Wang, Dong H Zhang, Bina Fu","doi":"10.1021/acs.jpca.5c00449","DOIUrl":null,"url":null,"abstract":"<p><p>The reaction of <i>anti</i>-CH<sub>3</sub>CHOO with H<sub>2</sub>O is a crucial atmospheric process, resulting in the end products CH<sub>3</sub>COOH + H<sub>2</sub>O through the dissociation of the intermediate hydroxyethyl hydroperoxide (CH<sub>3</sub>CH(HO)OOH, HEHP). Based on an accurate full-dimensional PES, we have obtained detailed dynamics information for this reaction through quasi-classical trajectory simulations. We report two reaction mechanisms for the CH<sub>3</sub>COOH + H<sub>2</sub>O product channel: one involving a direct mechanism through the transition state and the other an intriguing OH roaming mechanism. The roaming pathway proceeds via the dissociation of HEHP into OH and the hydroxyethoxy radical (CH<sub>3</sub>CH(HO)O, HEO), where the OH radical roams near HEO and abstracts a hydrogen atom, subsequently forming H<sub>2</sub>O and CH<sub>3</sub>COOH. The presence of this roaming pathway significantly increases the yield of CH<sub>3</sub>COOH + H<sub>2</sub>O. This work provides new dynamical support for the study of the <i>anti</i>-CH<sub>3</sub>CHOO + H<sub>2</sub>O reaction and enriches our understanding of atmospheric chemistry.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4364-4373"},"PeriodicalIF":2.7000,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"OH Roaming as a Key Pathway in the Anti-CH<sub>3</sub>CHOO + H<sub>2</sub>O Reaction Yielding CH<sub>3</sub>COOH and H<sub>2</sub>O.\",\"authors\":\"Lijie Liu, Hao Wu, Yanlin Fu, Xiaoxiao Lu, Xingan Wang, Dong H Zhang, Bina Fu\",\"doi\":\"10.1021/acs.jpca.5c00449\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The reaction of <i>anti</i>-CH<sub>3</sub>CHOO with H<sub>2</sub>O is a crucial atmospheric process, resulting in the end products CH<sub>3</sub>COOH + H<sub>2</sub>O through the dissociation of the intermediate hydroxyethyl hydroperoxide (CH<sub>3</sub>CH(HO)OOH, HEHP). Based on an accurate full-dimensional PES, we have obtained detailed dynamics information for this reaction through quasi-classical trajectory simulations. We report two reaction mechanisms for the CH<sub>3</sub>COOH + H<sub>2</sub>O product channel: one involving a direct mechanism through the transition state and the other an intriguing OH roaming mechanism. The roaming pathway proceeds via the dissociation of HEHP into OH and the hydroxyethoxy radical (CH<sub>3</sub>CH(HO)O, HEO), where the OH radical roams near HEO and abstracts a hydrogen atom, subsequently forming H<sub>2</sub>O and CH<sub>3</sub>COOH. The presence of this roaming pathway significantly increases the yield of CH<sub>3</sub>COOH + H<sub>2</sub>O. This work provides new dynamical support for the study of the <i>anti</i>-CH<sub>3</sub>CHOO + H<sub>2</sub>O reaction and enriches our understanding of atmospheric chemistry.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\" \",\"pages\":\"4364-4373\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2025-05-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.5c00449\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/5/9 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.5c00449","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/5/9 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
OH Roaming as a Key Pathway in the Anti-CH3CHOO + H2O Reaction Yielding CH3COOH and H2O.
The reaction of anti-CH3CHOO with H2O is a crucial atmospheric process, resulting in the end products CH3COOH + H2O through the dissociation of the intermediate hydroxyethyl hydroperoxide (CH3CH(HO)OOH, HEHP). Based on an accurate full-dimensional PES, we have obtained detailed dynamics information for this reaction through quasi-classical trajectory simulations. We report two reaction mechanisms for the CH3COOH + H2O product channel: one involving a direct mechanism through the transition state and the other an intriguing OH roaming mechanism. The roaming pathway proceeds via the dissociation of HEHP into OH and the hydroxyethoxy radical (CH3CH(HO)O, HEO), where the OH radical roams near HEO and abstracts a hydrogen atom, subsequently forming H2O and CH3COOH. The presence of this roaming pathway significantly increases the yield of CH3COOH + H2O. This work provides new dynamical support for the study of the anti-CH3CHOO + H2O reaction and enriches our understanding of atmospheric chemistry.
期刊介绍：
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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