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用 B3LYP/6-31 1 G( d,p)密度泛函方法和高级电子相关的 CCSD( T) /6-31 1 G( 2 df,p)偶合簇法研究BH+ 2 与 C2 H2 反应势能面 .结果表明 :该势能面上存在 ( a) H2 B+· C2 H2 ,( b) HBCHCH2 + ,( c) H2 BCCH+ 2 和( d) H2 · BHCCH+ 四种异构体 ,其中 ( b)能量最低且在动力学上最稳定 ,( a) ,( c)和 ( d)在动力学上均不稳定 ;BH+ 2 通过对 C2 H2 的分步亲电加成以及随后的氢迁移和 H2 消除等反应形成离解产物 HBCCH+ +H2 ,该反应不需要活化能且大量放热 .计算结果有助于深入了解 BH+ 2 等缺电子硼氢正离子的反应行为
The potential energy surface of the reaction between BH + 2 and C2H2 was studied by using B3LYP / 6-31 1 G (d, p) density functional theory and the advanced electron-related CCSD (T) / 6-31 1 G (2 df, p) The results show that: (a) H2 B + · C2 H2, (b) HBCHCH2 +, (c) H2 BCCH + 2 and (d) H2 · BHCCH + (A), (c) and (d) are kinematically unstable; BH + 2 is formed by the step-wise electrophilic addition of C2H2 and subsequent reactions such as hydrogen transfer and H2 elimination The dissociation product HBCCH + + H2, the reaction does not require activation energy and a lot of exothermic. The calculation results help to understand the reaction behavior of BH +2 and other electron deficient boron hydride ions