Sun Wei-Ming, Fan Li-Tao, Li Ying, Liu Jia-Yuan, Wu Di, Li Zhi-Ru
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University , Changchun 130023, People's Republic of China.
Inorg Chem. 2014 Jun 16;53(12):6170-8. doi: 10.1021/ic500655s. Epub 2014 May 30.
A new series of superalkali-based alkalides, i.e., Li3(+)(calix[4]pyrrole)M(-), Li3O(+)(calix[4]pyrrole)M(-), and M3O(+)(calix[4]pyrrole)K(-) (M = Li, Na, and K), have been theoretically designed and investigated by means of density functional theory computations. These species have diverse structural isomers, in which the embedded superalkali units maintain their identities and prefer the horizontal orientation over the vertical one. All the proposed alkalides exhibit considerable first hyperpolarizabilities (β0) up to 34,718 au. Especially, a prominent M(-) atomic number dependence of (hyper)polarizabilities is observed for the Li3(+)(calix[4]pyrrole)M(-) and Li3O(+)(calix[4]pyrrole)M(-) compounds. Besides, the dependence of the nonlinear optical response of such alkalides on the species of involved superalkalis is also investigated. We hope that this work will promote further application of superalkalis and, on the other hand, attract more research interest and efforts in exploring new, unconventional alkalides.
通过密度泛函理论计算，理论设计并研究了一系列新型基于超碱的碱化物，即Li3(+)(杯[4]吡咯)M(-)、Li3O(+)(杯[4]吡咯)M(-)和M3O(+)(杯[4]吡咯)K(-)（M = Li、Na和K）。这些物种具有多种结构异构体，其中嵌入的超碱单元保持其特性，并且相对于垂直取向更喜欢水平取向。所有提出的碱化物都表现出高达34718 au的可观的第一超极化率(β0)。特别是，对于Li3(+)(杯[4]吡咯)M(-)和Li3O(+)(杯[4]吡咯)M(-)化合物，观察到(超)极化率对M(-)原子序数有显著依赖性。此外，还研究了此类碱化物的非线性光学响应与所涉及超碱种类的关系。我们希望这项工作将促进超碱的进一步应用，另一方面，吸引更多研究兴趣并推动在探索新型非常规碱化物方面做出更多努力。
