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(Super)alkali atoms interacting with the σ electron cloud: a novel interaction mode triggers large nonlinear optical response of M@P4 and M@C3H6 (M=Li, Na, K and Li3O)

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Abstract

Under high-level ab initio calculations, the geometrical structures and nonlinear optical properties of M@P4 (M=Li, Na, K and Li3O) and M@C3H6 (M=Li and Li3O) were investigated; all were found to exhibit considerable first hyperpolarizabilities (18110, 1440, 22490, 50487, 2757 and 31776 au, respectively). The computational results revealed that when doping the (super)alkali atom M into the tetrahedral P4 molecule, the original dual spherical aromaticity of the P4 moiety is broken and new σ electron cloud is formed on the face of P4 part interacting with the M atom. It was found that interaction of the (super)alkali atom with the σ electron cloud is a novel mode to produce diffuse excess electrons effectively to achieve a considerable β 0 value. Further, beyond the alkali atom, employing the superalkali unit can be a more effective approach to significantly enhance the first hyperpolarizability of the systems, due to the much lower vertical ionization potential. These results were further supported by the case of the (super)alkali atom interacting with the cyclopropane C3H6 molecule with its typical σ aromatic electron cloud. Moreover, the β 0 values of the M@P4 series are nonmonotonic dependent on alkali atomic number, namely, 1440 au (M = Na) < 18110 au (Li) < 22490 au (K), inferring that the distance between the alkali atom and the interacting surface with the σ electron cloud in P4 is a crucial geometrical factor in determining their first hyperpolarizabilities. These intriguing findings will be advantageous for promoting the design of novel high-performance nonlinear optical materials.

A new mode through a (super)alkali atom interacting with the σ electron cloud is proposed to introduce diffuse excess electrons, which leads to large first hyperpolarizability (β 0) in the sampled M@P4 and M@C3H6 (M=Li, Na, K and Li3O) series. Doping the superalkali atom could be an effective approach to enhancing the β 0 value of these systems because of the much lower vertical ionization potential

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Acknowledgments

This work was supported by National Natural Science Foundation of China (21103065, 21373099, 21073075 and 21173097), National Basic Research Program of China (973 Program) (2012CB932800), and the Ministry of Education of China (20110061120024 and 20100061110046). We acknowledge the High Performance Computing Center (HPCC) of Jilin University for supercomputer time.

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  1. The State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, People’s Republic of China

    Xingang Zhao, Guangtao Yu, Xuri Huang, Wei Chen & Min Niu

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Correspondence to Guangtao Yu or Wei Chen.

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The online version of this article contains supplementary material of discussions on the impact of the different exchange-correlation potentials on the computed TDDFT results (Table S1), which is available to authorized users.

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Zhao, X., Yu, G., Huang, X. et al. (Super)alkali atoms interacting with the σ electron cloud: a novel interaction mode triggers large nonlinear optical response of M@P4 and M@C3H6 (M=Li, Na, K and Li3O). J Mol Model 19, 5601–5610 (2013). https://doi.org/10.1007/s00894-013-2041-3

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