3 years ago

Effects of the Cage Number and Excess Electron Number on the Second Order Nonlinear Optical Response in Molecular All-Metal Electride Multicage Chains

Effects of the Cage Number and Excess Electron Number on the Second Order Nonlinear Optical Response in Molecular All-Metal Electride Multicage Chains
Rong-Lin Zhong, Zhi-Ru Li, Zhong-Jun Zhou, Hui Yang, Dan Yu, Di Wu, Hui-Min He, Ying Li
For novel all-metal electride, multicage chain structures [(Ni@Ge9) Ca3]n (n = 1–4) with all real frequencies are obtained theoretically for the first time. In the structure of n = 1, the Ni@Ge9 metal cage as the shortest chain skeleton is surrounded by nonbridge Ca atoms. In the structures of n = 2–4, Ni@Ge9 metal cages are connected by bridge Ca atom pair(s) forming new hybrid multicage chain skeletons surrounded by nonbridge Ca atoms. And interesting pull–push electron relay occurs. The chain skeleton pulls valence electrons from nonbridge Ca atoms forming skeleton polyanion, and then formed polyanion pushes remaining valence electrons of the Ca atoms forming excess electrons. The excess electron numbers are Ne = 2, 0, 4, 4 for n = 1, 2, 3, 4, respectively. It is shown that these structures with excess electrons are molecular all-metal electride multicage chains, unexpectedly, and the structure (n = 2) without excess electron is a Ca salt. For nonlinear optical (NLO) response, the electride chains have large static first hyperpolarizabilities (β0e). And β0e increases strongly from 9321 (n = 1, Ne = 2) to 54232 au (n = Ne = 4), which exhibits that significant cage number and excess electron number effects on NLO response. Besides electronic contribution (β0e) to static first hyperpolarizability, the large vibrational contribution (β0nr) are also revealed, and the ratios of β0nr0e are 0.18–1.17. Moreover, the frequency-dependent values βe(−2ω; ω, ω) and βe(−ω; ω, 0) have also been estimated. Especially, the evolutions of prominent cage number effects on β0e, β0nr, βe (−2ω; ω, ω) and βe(−ω; ω, 0) are similar. Then a new design strategy of enhancing NLO response by increasing metal-cage number is obtained. Hence, these molecular all-metal electride multicage chains as novel nanorods are promising new NLO nanomaterials.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b06464

DOI: 10.1021/acs.jpcc.7b06464

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