物理化学学报 >> 1985, Vol. 1 >> Issue (06): 504-510.doi: 10.3866/PKU.WHXB19850602

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H2和I2反应的赝势法量子化学研究

傅孝愿; 金俗谦   

  1. 北京师范大学化学系量子化学研究室
  • 收稿日期:1985-01-14 修回日期:1985-04-15 发布日期:1985-12-15

A THEORETICAL STUDY ON THE REACTION BETWEEN HYDROGEN AND IODINE

Fu Xiaoyuan; Jin Suqian   

  1. Dept. of Chemistry, Beijing Normal University, Beijing, China
  • Received:1985-01-14 Revised:1985-04-15 Published:1985-12-15

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摘要： 用赝势价轨道从头算方法并采用双组态行列式波函数, 找出了H_2与两个碘原子反应形成的直线型过渡态的几何构型。根据这个构型, 利用CIPSI程序进行了微扰CI计算, 得到了反应活化能的近似值。根据所得到的结果对H_2与I_2反应的机理进行了探讨, 支持了三分子反应的观点。

Abstract: The termolecular reaction H_2+2I→2HI has been studied by quantum chemi- cal pseudopotential ab initio method. The transition state was assumed to be li- near:
I ——R_2 H ——R_1 H ——R_2 I
The reaction system was represented by a wave function consisting of two confi- gurations, i.e.
ψ=C_1ψ1+C_2ψ_2
where ψ_1 and ψ_2 are determinants describing the electronic state of reactant and product respectively. By solving a second order secular equation for fixed values of R_1 and R_2, we can obtain a point on the potential energy surface. Keeping R_1 constant and varying R_2 (or vice versa), an energy ...