【摘要】 构建了LDHs主客体作用模型,采用混合密度泛函B3LYP方法,在6-31G(d)水平上进行结构优化和频率分析,然后分别用6-31G(d)和6．311++G(d,p)基组计算主客体相互作用能,从几何参数、电荷布居、前线轨道、能量以及热力学参数等角度探讨LDHs主体层板与卤素阴离子(F-,Cl-)间的超分子作用．计算结果表明,LDHs主体层板复合卤素阴离子是一个自发过程．LDHs主客体间存在着较强的超分子作用,主要包括静电和氢键作用,相互作用能分别为-592．45和-444．01 kJ·mol-1．LDHs主体层板与卤素阴离子的前线轨道发生作用,电子容易从卤素阴离子的HOMO向层板的LUMO转移,形成的组装产物Mg6Al(OH)14+:F-比Mg6Al(OH)14+:Cl-稳定．更多还原

【Abstract】 An interaction model between the host and the guest of layered double hydroxides (LDHs) is proposed. The structure parameters and vibration frequencies of LDHs are calculated using density functional theory B3LYP method at the 6-31G(d) level, and the interaction energies are evaluated with the B3LYP/6-31G(d) and B3LYP/6-311++ G(d, p) methods, respectively. The supra-molecular interaction between a host layer and a guest anion has been investigated by analyzing the geometric parameters, charge population, frontier orbital, interaction energy, and thermodynamic parameters. The results show that the binding process of the host layer and halide anion is spontaneous. There is a strong supra-molecular interaction between the host layer and a guest anion F- or Cl-. The host-guest interaction energies of Mg6Al(OH)14+:F- and Mg6Al(OH)14+:Cl- are -592.45 and -444.01 kJ·mol-1, respectively. Supra-molecular interactions are resulted mainly from the electrostatic interaction and the hydrogen-bond. The frontier orbital of the host layer interacts with that of the guest anion, and the electron is transferred from HOMO of halide anion to LUMO of the host layer. Moreover, Mg6Al(OH)14+:F- is more stable than the Mg6Al(OH)14+:Cl- .更多还原