Superatom Compounds under Oriented External Electric Fields: Simultaneously Enhanced Bond Energies and Nonlinear Optical Responses
Superatom Compounds under Oriented External Electric Fields: Simultaneously Enhanced Bond Energies and Nonlinear Optical Responses
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定向外部电场下的超原子化合物：同时增强的键能和非线性光学响应
DOI：
10.1021/acs.jpcc.8b01896
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发表时间：
2018-03
影响因子：
3.7
通讯作者：
Li Zhi-Ru
中科院分区：
文献类型：
--
作者：
Sun Wei-Ming;Li Chun-Yan;Kang Jie;Wu Di;Li Ying;Ni Bi-Lian;Li Xiang-Hui;Li Zhi-Ru
最近的研究表明，定向外电场（OEEF）可以作为未来的智能试剂和效应器在化学中。因此，研究了OEEF对三种典型超原子化合物的几何结构、电子性质、成键性质和非线性光学响应的影响，本文采用从头计算方法对（NLi_4）（BF_4）和（BLi_6）X（X = BeF_3和BF_4）进行了系统的研究。计算结果表明，在相同的OEEF下，（NLi 4）（BF 4）具有与传统碱金属卤化物几乎相同的性能。结果表明，沿着电荷转移方向（NLi 4 → BF 4），OEEF从零增加到临界外电场（Fc），可以逐渐提高（NLi 4）（BF 4）的垂直电离势、键能和第一超极化率.特别是，通过将OEEF从0增加到121 × 10-4，（NLi 4）（BF 4）的第一超极化率从2.84 × 103大大增加到1.36 × 107 Au（4790倍）.
It has recently been demonstrated that oriented external electric fields (OEEFs) can serve as future smart reagents and effectors in chemistry. Consequently, the effect of OEEFs on the geometric structures, electronic properties, bonding properties, and NLO responses of three typical superatom compounds, i.e., (NLi4)(BF4) and (BLi6)X (X = BeF3 and BF4) has been systemically investigated by ab initio computations in this work. The computational results reveal that the (NLi4)(BF4) possesses almost the same performance as the traditional alkali metal halide under the same OEEFs. It is found that the vertical ionization potential, bond energy, and first hyperpolarizability of (NLi4)(BF4) can be gradually enhanced by increasing the imposed OEEF from zero to the critical external electric field (Fc) along the charge transfer direction (NLi4 → BF4). In particular, the first hyperpolarizability of (NLi4)(BF4) is greatly enlarged from 2.84 × 103 to 1.36 × 107 au (4790-fold) by increasing OEEF from 0 to 121 × 10–4 ...