{"title":"15种C7H7+阳离子异构化的速率系数和Arrhenius参数的计算研究","authors":"Kiew S Kharnaior, Shemphang Hynniewta","doi":"10.1007/s12039-025-02391-w","DOIUrl":null,"url":null,"abstract":"<div><p>In a previous communication (<i>Comp. Theor. Chem.</i> <b>1091</b> (2016) 150), concerted isomerization reactions of 15 C<sub>7</sub>H<sub>7</sub><sup>+</sup> cations in the gas phase had been studied. The present study deals with the kinetics of these concerted isomerization reactions using the M06-2X functional. From the potential energy profiles of these reactions, the rate coefficients are estimated by using transition state theory along with the estimation of Wigner’s empirical transmission coefficient for quantum tunnelling. The rate coefficient values are calculated over a temperature range of 200–500 K, where the Arrhenius activation energies, along with the pre-exponential factors, are determined for each of these reactions.</p><h3>Graphical abstract</h3><p>The graphical abstract highlight the two representative isomerisation reactions of bicyclo[3.2.0]heptadienyl cation <b>4</b> to tropyl cation <b>1</b> (global minimum) by C-C σ-bond collapse to π-bond via transition state <b>TS1</b> and <i>o</i>-tolyl cation <b>5</b> to benzyl cation <b>2</b> by 1,3-hydride shift via <b>TS4</b>.</p>\n<div><figure><div><div><picture><img></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 3","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Rate coefficients and Arrhenius parameters for the isomerization of 15 selected C7H7+ cations: A computational study\",\"authors\":\"Kiew S Kharnaior, Shemphang Hynniewta\",\"doi\":\"10.1007/s12039-025-02391-w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In a previous communication (<i>Comp. Theor. Chem.</i> <b>1091</b> (2016) 150), concerted isomerization reactions of 15 C<sub>7</sub>H<sub>7</sub><sup>+</sup> cations in the gas phase had been studied. The present study deals with the kinetics of these concerted isomerization reactions using the M06-2X functional. From the potential energy profiles of these reactions, the rate coefficients are estimated by using transition state theory along with the estimation of Wigner’s empirical transmission coefficient for quantum tunnelling. The rate coefficient values are calculated over a temperature range of 200–500 K, where the Arrhenius activation energies, along with the pre-exponential factors, are determined for each of these reactions.</p><h3>Graphical abstract</h3><p>The graphical abstract highlight the two representative isomerisation reactions of bicyclo[3.2.0]heptadienyl cation <b>4</b> to tropyl cation <b>1</b> (global minimum) by C-C σ-bond collapse to π-bond via transition state <b>TS1</b> and <i>o</i>-tolyl cation <b>5</b> to benzyl cation <b>2</b> by 1,3-hydride shift via <b>TS4</b>.</p>\\n<div><figure><div><div><picture><img></picture></div></div></figure></div></div>\",\"PeriodicalId\":616,\"journal\":{\"name\":\"Journal of Chemical Sciences\",\"volume\":\"137 3\",\"pages\":\"\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-08-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Sciences\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s12039-025-02391-w\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Sciences","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s12039-025-02391-w","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Rate coefficients and Arrhenius parameters for the isomerization of 15 selected C7H7+ cations: A computational study
In a previous communication (Comp. Theor. Chem.1091 (2016) 150), concerted isomerization reactions of 15 C7H7+ cations in the gas phase had been studied. The present study deals with the kinetics of these concerted isomerization reactions using the M06-2X functional. From the potential energy profiles of these reactions, the rate coefficients are estimated by using transition state theory along with the estimation of Wigner’s empirical transmission coefficient for quantum tunnelling. The rate coefficient values are calculated over a temperature range of 200–500 K, where the Arrhenius activation energies, along with the pre-exponential factors, are determined for each of these reactions.
Graphical abstract
The graphical abstract highlight the two representative isomerisation reactions of bicyclo[3.2.0]heptadienyl cation 4 to tropyl cation 1 (global minimum) by C-C σ-bond collapse to π-bond via transition state TS1 and o-tolyl cation 5 to benzyl cation 2 by 1,3-hydride shift via TS4.
期刊介绍：
Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.
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