The nine optimized structures of the organic M+@ H6Aza222M'- ·2MeNH2(M, M'=Li, Na, K) alkalides with real frequencies were obtained via the density functional theory (DFT) with the B3LYP functional and the 6-31G basis set. It was found that the inside M atom showed a tendency to move towards one side of the H6Aza222 cage with decreasing atomic number. The BHandHLYP method was employed to calculate the nonlinear optical(NLO) properties of these species. The results show that the M+@ H6Aza222M'-·2MeNH2 alkalides exhibit dramatically large value of first hyperpolarizabilities (β0) , and the largest value of /30 is 1280342 a. u. for the Na+@ H6Aza222K-·2MeNH2 species. In addition, we also found that the first hyperpolarizabilities of M+@ H6Aza222M'-·2MeNH2 increased with the increasing atomic number of alkali metal atom(M') which resided outside the H6Aza222 complexant.%采用B3 LYP/6 -31G方法优化得到具有有机笼状配体的碱金属化物M+@ H6Aza222M′-·2MeNH2(M,M′=Li,Na,K)的9个实频结构,并发现配体内部的碱金属原子M的位置随其原子序数的逐渐减小而具有偏向笼状配体一侧的趋势.在优化的结构基础上,使用BHandHLYP方法计算了该体系的非线性光学性质.结果表明,该体系具有很大的一阶超极化率(β0),其中Na+@ H6 Aza222K-·2MeNH2的一阶超极化率高达1280342 a.u.,且体系的β0值随着配体外部的碱金属M′的原子序数的增大呈单调递增趋势.
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