Intra- and Intermolecular Charge Transfer in a Novel Dimer: Cooperatively Enhancing Second-Order Optical Nonlinearity,The Journal of Physical Chemistry C

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Intra- and Intermolecular Charge Transfer in a Novel Dimer: Cooperatively Enhancing Second-Order Optical Nonlinearity
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpcc.7b08172
Feng-Wei Gao ₁ , Rong-Lin Zhong ₂ , Hong-Liang Xu ₁ , Zhong-Min Su ₁

Affiliation

Based on s-indaceno[1,2,3-cd;5,6,7-c′d′]diphenalene (1) consisting of two phenalenyl moieties, the monomer 2 and its dimer 2₂ are designed by boron and nitrogen atoms substituting the central carbon atoms of phenalenyl moieties. Calculated energy decompose analysis (EDA) shows that the orbital interaction for 2₂ possesses a large attractive contribution of −18.31 kcal mol^–1, which is dominated by the π–π stacking interaction between the upper and the lower π-conjugated units. Interestingly, the natural population analysis (NPA) charge and the transition density matrix (TDM) show that both intramolecular charge transfer and intermolecular charge transfer (CT) exist in 2₂. Further, the first hyperpolarizability (β_tot = 4.56 × 10⁴ au) of 2 with intramolecular CT is greatly larger than that of reported molecule 3 (5.45 × 10³ au) with intermolecular CT. Significantly, 2₂ exhibits the largest β_tot value to be 1.42 × 10⁵ au, which is caused by combining the intra- and intermolecular CT transitions (β_x = 1.40 × 10⁵ au and β_z = 2.27 × 10⁴ au). Correspondingly, highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) (intramolecular CT) in the low-energy electronic transition of 2₂ is 68%, while HOMO → LUMO + 1 (intermolecular CT) is 18%, which demonstrates that the intramolecular CT effect on the β_tot value is stronger than the case of the intermolecular CT effect. The present work might provide rich insight into designing and developing potential second-order optical nonlinearity materials with inter- and intramolecular CT characters.

中文翻译：

新型二聚体的分子内和分子间电荷转移：协同增强二阶光学非线性

基于小号-indaceno [1,2,3- CD ; -4,5,6,7- Ç ' d '] diphenalene（1）由两个非那烯基部分的，单体2和其二聚体2 ₂由硼和氮原子而设计取代菲基部分的中心碳原子。计算的能量分解分析（EDA）表明，2 ₂的轨道相互作用具有−18.31 kcal mol ^–1的较大吸引力。，由上和下π共轭单元之间的π-π堆积相互作用决定。有趣的是，自然种群分析（NPA）电荷和跃迁密度矩阵（TDM）显示，分子内电荷转移和分子间电荷转移（CT）均存在于2 _2中。此外，分子内CT的第一个超极化率（_βtot = 4.56×10 ⁴ au）为2，远远大于分子间CT的报道的分子3（5.45×10 ³ au）。显着地，2 ₂的最大_βtot值为1.42×10 ⁵AU，这是通过结合胞内和分子间CT转变（β引起的_X = 1.40×10 ⁵的Au和β _ž = 2.27×10 ⁴ AU）。相应地，在低能电子跃迁2 _2中，最高占据分子轨道（HOMO）→最低未占据分子轨道（LUMO）（分子内CT）为68％，而HOMO→LUMO + 1（分子间CT）为18％，证明了分子内CT对_βtot值的作用比分子间CT作用强。目前的工作可能会提供丰富的见识，以设计和开发具有分子间和分子内CT特性的潜在的二阶光学非线性材料。

更新日期：2017-11-08

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