Theoretical Investigation On The First Hyperpolarizabilities Of M+@H(6)Aza222m '(-)Center Dot 2menh(2)(M,M '=Li, Na, K) Alkalides

The nine optimized structures of the organic M+@H(6)Aza(222)M'(-)center dot 2MeNH(2)(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 H(6)Aza222 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+@H(6)Aza222M'(-)center dot 2MeNH(2) alkalides exhibit dramatically large value of first hyperpolarizabilities (beta(0)), and the largest value of beta(0) is 1280342 a. u. for the Na+@H(6)Aza222K(-)center dot 2MeNH(2) species. In addition, we also found that the first hyperpolarizabilities of M+@H(6)Aza222M'(-)center dot 2MeNH(2) increased with the increasing atomic number of alkali metal atom(M') which resided outside the H(6)Aza222 complexant.