Static second hyperpolarizability of inverse sandwich compounds (M1–C5H5–M2) of alkali (M1 = Li, Na, K) and alkaline earth metals (M2 = Be, Mg, Ca)†,Physical Chemistry Chemical Physics

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Static second hyperpolarizability of inverse sandwich compounds (M1–C5H5–M2) of alkali (M1 = Li, Na, K) and alkaline earth metals (M2 = Be, Mg, Ca)†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-04-19 00:00:00 , DOI: 10.1039/c8cp01210e
Kaushik Hatua _{1,

2,

3,

4} , Avijit Mondal _{1,

2,

3,

4} , Prasanta K. Nandi _{1,

2,

3,

4}

Affiliation

In the investigated inverse sandwich complexes, charge transfer from alkali metal (M₁) led to aromatically stabilized Cp ring, which prevented further charge transfer from the alkaline earth metal (M₂). This electron push effect resulted in diffusion of electron density from the outermost “ns” subshell of alkaline earth metal. The alkaline earth metal is weakly bound to the alkali metal–C₅H₅ complex. The vertical ionization energy of the chosen M₁–Cp–M₂ complexes was smaller than that of the corresponding alkaline earth metals. Large second hyperpolarizability (10⁶–10⁸ a.u.) was obtained for the studied molecules. The correction due to the basis set superposition error (BSSE) in the calculated second hyperpolarizability was found to be small for larger systems, while it was rather significant for small systems. The MP4SDQ and CCSD results were in fair agreement, which indicates the necessity of higher order electron correlation treatment in the accurate description of second hyperpolarizability. Calculated dynamic second hyperpolarizabilities at 1064 nm were found to increase considerably for most of the chosen metal complexes.

中文翻译：

碱金属（M ₁ = Li，Na，K）和碱土金属（M ₂ = Be，Mg，Ca）的反三明治化合物（M ₁ –C ₅ H ₅ –M ₂）的静态第二超极化性†

在研究的逆三明治复合物中，碱金属（M ₁）的电荷转移导致了芳族稳定的Cp环，从而阻止了碱土金属（M ₂）的进一步电荷转移。这种电子推动效应导致电子密度从碱土金属的最外层“ ns”子壳中扩散出来。碱土金属与碱金属– C ₅ H _5配合物的结合较弱。所选的M ₁ -Cp-M ₂配合物的垂直电离能小于相应的碱土金属的垂直电离能。较大的第二超极化率（10 ⁶ –10 ⁸au）是针对所研究的分子而获得的。发现在计算的第二超极化率中，由于基组叠加误差（BSSE）而引起的校正对于较大的系统来说很小，而对于较小的系统来说却很重要。MP4SDQ和CCSD结果基本吻合，这表明在准确描述第二超极化性时必须进行高阶电子相关处理。对于大多数选定的金属配合物，发现在1064 nm处计算的动态第二超极化率显着增加。

更新日期：2018-04-19

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