Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers

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• 作者：Feiyu Yang ; Fuquan Deng ; Youshun Pan ; Zemin Tian ; Yingjia Zhang ; ^{yjzhang_xjtu@mail.xjtu.edu.cn" class="auth_mail" title="E-mail the corresponding author} ; Zuohua Huang ; ^{zhhuang@mail.xjtu.edu.cn" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Hexadienes ; Isomerization ; Transition state ; PES ; Rate constant
• 刊名：Chemical Physics Letters
• 出版年：2016
• 出版时间：16 October 2016
• 年：2016
• 卷：663
• 期：Complete
• 页码：66-73
• 全文大小：1318 K

文摘

The ground-state potential energy surface (PES) of isomerization philosophy of ten normal-chain hexadiene isomers is computed by density functional methods using the geometries optimized at B3LYP/6-311++G (d, p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization reactions by transition state theory (TST) in the temperature range of 500–2500 K. Difference of rate constant between each hexadiene isomer is interpreted through the PES and Ḣ atom transfer, and only 2,4-hexadiene readily fulfills cis-cis to trans-trans conformation conversion. All the conversions are kinetically interpreted from the PES and ST geometry.