H2和I2反应的赝势法量子化学研究

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。

A THEORETICAL STUDY ON THE REACTION BETWEEN HYDROGEN AND IODINE

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 IThe 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 ...