【摘要】 采用从头算程序对MgO表面 3种不同配位位置吸附Cl2 的构型进行优化 ,并用扩展休克尔紧束缚 (EHT)晶体轨道方法对MgO的缺陷和不规则表面吸附Cl2的可能构型进行能带计算 ,讨论了吸附前后能带组成和成键性质的变化。研究表明 :MgO表面吸附Cl2 将更趋向于吸附在O原子上而非Mg原子上 ,而且在 3种配位中MgO表面三配位氧最有利于吸附Cl2 ;吸附时 ,电子从O原子转移到Cl2 分子的反键轨道 ,但是各种吸附构型的MgO表面对Cl2 的吸附作用均比较微弱 ,是典型的物理吸附。更多还原

【Abstract】 Using the geometric configuration optimized from ab initio calculation, the electronic structures of Cl₂ adsorption on MgO（001） defective and irregular surfaces were studied by EHT crystal orbital method. The characteristics of bands have been discussed. The results of the optimization have proved that Cl₂ is preferable to bind over oxygen sites. Moreover, Cl₂ binds at Mg（3C） cations corner sites considerably stronger than at regular Mg（5C） and Mg（4C） sites. The charge redistributions in the Cl₂ molecule and in the substrate are considered. The magnesium vacancy of MgO（001） surface is more beneficial to Cl₂ adsorption and decompose on the surface than other configurations. It is proved that the interactions between the Cl₂ /surface are weak physisorption.\;更多还原