Molecular Tailoring by Furan and Thiophene Heterocycles to Optimize Nonlinear Optical and Photovoltaic Efficiency

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-05-13 DOI:10.1016/j.jphotochem.2025.116496

Shabbir Muhammad , Jannat Bibi , Bakhet A. Alqurashy , Saleh S. Alarfaji , Abul Kalam , Aijaz Rasool Chaudhry , Abdullah G. Al-Sehemi

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Abstract

Modern advancements in optoelectronics, laser frequency modulation, quantum computing, and telecommunications rely on efficient nonlinear optical (NLO) materials. This study presents a computational design and analysis of a new series of organic acceptor–donor-acceptor compounds (1a to 3b), focusing on the influence of thiophene and furan heterocyclic ring arrangements on their NLO response. Quantum chemical calculations were performed to evaluate the linear polarizabilities (α) and third-order nonlinear polarizabilities < γ > . Among the series, compound 2b exhibited the highest < γ > of 3744 × 10^-36 esu, which is ∼ 486 times greater than the benchmark NLO molecule of p-nitroaniline (p-NA) computed at the same theoretical level. Additionally, 3a showed the highest linear isotropic polarizability (α_iso) of 163 × 10^-24 esu, while 1b had the highest anisotropic polarizability (α_aniso) of 182.6 × 10^-24 esu. Solvent effects using the COSMO model revealed a ∼ 2 to ∼ 3-fold enhancement in < γ > for selected derivatives (1b, 2a, and 3a). The frequency-dependent < γ > of 2b was calculated at the common laser wavelengths (1064 nm, 1529 nm, and 1947 nm), yielding < γ > values of 4034 × 10^-36, 4457 × 10^-36, and 6034 × 10^-36 esu, respectively. TD-DFT analysis revealed that 2b possesses the lowest transition energy of 2.596 eV, contributing to its enhanced NLO response. Frontier molecular orbital (FMO) analysis indicated a narrow crucial orbital energy gap (2.45 eV), confirming strong intramolecular charge transfer (ICT). Furthermore, photovoltaic parameters also suggest that 1b has the most favorable dye regeneration energy and open-circuit voltage. These findings highlight the potential of the entitled compounds for advanced NLO and optoelectronic applications.

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呋喃和噻吩杂环分子裁剪优化非线性光学和光伏效率

光电子学、激光调频、量子计算和电信的现代进步依赖于高效的非线性光学（NLO）材料。本研究提出了一系列新的有机受体-供体-受体化合物（1a至3b）的计算设计和分析，重点关注噻吩和呋喃杂环排列对其NLO响应的影响。用量子化学方法计算了线性极化率（α）和三阶非线性极化率<；γ祝辞。其中化合物2b表现出最高的<；γ祝辞为3744 × 10-36 esu，这是在相同理论水平下计算的对硝基苯胺（p-NA）基准NLO分子的约486倍。3a的线性各向异性极化率（αiso）最高，为163 × 10-24 esu，而1b的各向异性极化率（αaniso）最高，为182.6 × 10-24 esu。使用COSMO模型的溶剂效应显示，<；γ祝辞对于选定的导数（1b， 2a和3a）。频率相关的<；γ祝辞在常用激光波长（1064 nm， 1529 nm和1947 nm）下计算2b，得到<；γ祝辞值分别为4034 × 10-36、4457 × 10-36、6034 × 10-36 esu。TD-DFT分析表明，2b的跃迁能最低，为2.596 eV，这有助于增强其NLO响应。前沿分子轨道（FMO）分析表明，临界轨道能隙较窄（2.45 eV），证实了较强的分子内电荷转移（ICT）。此外，光伏参数也表明，1b具有最有利的染料再生能量和开路电压。这些发现突出了这些化合物在先进的NLO和光电子应用方面的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Photochemistry and Photobiology A-chemistry 化学-物理化学

CiteScore

7.90

自引率

7.00%

发文量

580

审稿时长

48 days

期刊介绍： JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds. All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor). The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.