[Li…X]e-[1](X=FH,OH2, NH3)的光电性质从头算

在MP2理论水平上采用6-311G基组系列计算了一价阴离子van der Waals复合物Li…X]e-1](X=FH, OH2, NH3)的偶极矩(μ)、平均极化率(α)以及平均一阶超极化率(β), 讨论了基组效应和电子相关效应对计算结果的影响, 比较了价电子对复合物一阶超极化率的贡献. 在MP4(SDQ)/6-311++G(2df, 2pd)水平上计算得到Li…FH]e-1]的μ=2.5633 a.u., α=1.0476×10³ a.u., β=1.0948×10⁵ a.u.；Li…OH2]e-1] 的μ=2.3204 a.u., α=1.2201×10³ a.u., β=2.1410×10⁵ a.u.；Li…NH3]e-1]的μ=2.4687 a.u., α=1.4817×10³ a.u., β=3.4040×10⁵ a.u.. 计算结果表明, 三种一价阴离子复合物分子均具有非常大的一阶超极化率, 而一个价电子对复合物的一阶超极化率的贡献超过1.0×10⁵ a.u..

Ab Initio Study on Optoelectronic Properties of [Li…X]e-[1] (X=FH, OH2, NH3)

The dipole moment(μ), polarizability(α) and the first hyperpolarizability(β) of van der Waals complexes anion Li…X]e-1](X=FH, OH2, NH3) were calculated by using ab initio methods with 6-311G basis set series at MP2 level. We also discussed the contribution of the effect of basis set and the electronic correlation on the dipole moment, polarizability and the first hyperpolarizability, and compared the contributions of valence electrons to the first hyperpolarizability. The values of dipole moment, polarizability and the first hyperpolarizability of three complexes anion calculated with MP4(SDQ)/6-311++G(2df, 2pd) are: μ=2.5633 a.u., α=1.0476×10³ a.u., β=1.0948×10⁵ a.u. for Li…FH]e-1], μ=2.3204 a.u., α=1.2201×10³ a.u., β=2.1410×10⁵ a.u. for Li…OH2]e-1] and μ=2.4687 a.u., α=1.4817×10³ a.u., β= 3.4040×10⁵ a.u. for Li…NH3]e-1], respectively. The results showed that all the three complexes anion had huge first hyperpolarizability, andthe contributionof one valence electron tothe first hyperpolarizabilitywasmore than1.0×10⁵ a.u..