Electronic Absorption Spectra and Third-Order Nonlinear Optical Property of Dinaphtho[2,3-b:2’,3’-d]Thiophene-5,7,12,13- Tetraone (DNTTRA) and Its Phenyldiazenyl Derivatives: DFT Calculations

• 作者: Hongping Li Yonghua Guan Yuan Li Yujin Zhang Zhanrong He Ziran Chen
• 来源期刊: 计算化学(英文)
• 学科: 化学
• 关键词: AZOBENZENE Dinaphtho[2 3-b:2’ 3’-d]Thiophene-5 7 12 13-Tetraone Density Functional Theory Electronic Absorption Spectra Third-Order Nonlinear Optical Property
• 年，卷（期）: 2020,（4）
• 页码范围: 43-60
• 页数: 18页
• 分类号: O62

摘要

Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10⁷ atomic units (10^{<span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33} esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH₃)₂ or -NHCH₃) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.