Scholarlink

<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> Graphical abstract <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> <p></p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Rate coefficients and Arrhenius parameters for the isomerization of 15 selected C7H7+ cations: A computational study

  • 期刊论文

  • 发表日期：

    2025年8月20日

查看全文
  • Kiew S Kharnaior,
  • Shemphang Hynniewta

摘要

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.