碱金属化物M^+aza222M′^-(M,M′=Li,Na,K)的结构及非线性光学性质

Structures and Nonlinear Optical Properties of the Alkalides M^+aza222M′^-(M,M′=Li,Na,K)

采用密度泛函理论(DFT)B3LYP方法得到具有有机穴状配体的碱金属化物M+aza222M′-(M,M′=Li,Na,K)的几何结构.并使用了BHandHLYP方法计算了此体系的非线性光学(NLO)性质.结果表明:该体系具有很大的一阶超极化率(β0),对于Li+aza222K-体系,β0值达到1.0×106a.u.;体系的β0值及配体aza222内外的碱金属之间距离与碱金属的原子序数均存在着依赖关系.通过与其它碱金属化物的β0值对比发现,aza222配体能够显著增大碱金属化物的一阶超极化率.

Using density functional theory with the B3LYP functional,the optimized structures of the organic alkalides M ＋ aza222M′ - （M,M′=Li,Na,K,and aza222=Azacryptand[2.2.2]）were calculated.The nonlinear optical（NLO）properties of these species were calculated by the BHandHLYP method.The results indicate that the M ＋ aza222M′ - alkalides exhibit very large first hyperpolarizabilities（β 0 ）up to 1.0×10 6 a.u.（for M=Li,M′=K）.Both the first hyperpolarizabilities and the M-M′distances of M ＋ aza222M′ - were found to depend on the atomic number of the alkali metal atom M（M′）.By comparing theβ 0 values of various organic alkalides,aza222 was found to be preferable to the previously investigated complexants in enhancing the first hyperpolarizabilities of alkalides.