Development of highly efficient nonlinear optical materials based on alkali and superalkali metals-doped Li12F12 nanocages for advanced electro-optic applications

IF 2.1 4区材料科学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Nanoparticle Research Pub Date : 2025-01-17 DOI:10.1007/s11051-025-06219-z

Aneela Ahmad, Junaid Yaqoob, Muhammad Usman Khan, Mazhar Amjad Gilani, Muhammad Adnan Ayub, Omaid Ullah Anwar, Abrar Ul Hassan, Tansir Ahamad

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Abstract

Nonlinear optical (NLO) materials have gained popularity in the research world due to their numerous applications including optoelectronics, biosensors, lasers, and photonics. In this research, the theoretical study of Li₁₂F₁₂ nanocage doped with alkali and superalkali metal atoms is examined for the first time. DFT calculations are used to explore the electronics, stability, geometric, and nonlinear properties. The stability of designed isomers is predicted by the negative interaction energy values, with an isomer of Li₃O@ Li₁₂F₁₂ nanocage exhibiting the higher interaction energy (E_b) of − 49.46 kcal/mol. Doping Li₁₂F₁₂ nanocage with alkali (A) and superalkali (SA) decreased the HOMO–LUMO band gap. For doped isomers, a reduction in the energy gap up to 0.88 eV has been observed for K₃O@ Li₁₂F₁₂ nanocage which improves the NLO behavior. The maximum first hyperpolarizability value of designed isomers is 4.99 × 10⁵ au (VII-K₃O). NBO and DOS spectra are used to evaluate the charge transfer, the contribution of various parts, and their interactions. NCI analysis is used to perform different types of interactions between Li₁₂F₁₂ nanocage and alkali (Li, Na, K)-superalkali (Li₃O, Li₄N, K₃O, Na₃O). According to the TD-DFT calculations, complexes have λ_max in the near IR and visible region. The QTAIM analysis revealed weak covalent interactions except Na₃O and Li₄N complexes. This research may provide a path for the development of stable Li₁₂F₁₂ nanocage isomers, which will serve as essential building blocks for highly effective NLO materials.

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基于碱金属和超碱金属掺杂Li12F12纳米笼的高效非线性光学材料的开发，用于先进电光应用

非线性光学（NLO）材料由于其在光电子、生物传感器、激光和光子学等领域的广泛应用而在研究领域得到了广泛的应用。本研究首次对掺杂碱金属和超碱金属原子的Li12F12纳米笼进行了理论研究。DFT计算用于探索电子，稳定性，几何和非线性性质。用负相互作用能值预测了所设计异构体的稳定性，其中li30 @ Li12F12纳米笼的异构体具有较高的相互作用能（Eb），为- 49.46 kcal/mol。用碱(A)和超碱（SA）掺杂Li12F12纳米笼减小了HOMO-LUMO带隙。对于掺杂的异构体，k30 @ Li12F12纳米笼的能隙减少了0.88 eV，这改善了NLO行为。所设计的同分异构体第一超极化率最大值为4.99 × 105 au （vii - k30）。NBO和DOS谱用于评价电荷转移、各部分的贡献以及它们之间的相互作用。采用NCI分析方法研究了Li12F12纳米笼与碱（Li, Na， K）-超碱（li30o, Li4N, k30o, na30o）之间不同类型的相互作用。根据TD-DFT计算，配合物在近红外和可见光区域具有λmax。QTAIM分析显示，除na30o和Li4N配合物外，其他共价相互作用较弱。这项研究可能为开发稳定的Li12F12纳米笼异构体提供了一条途径，这将成为高效NLO材料的重要组成部分。图形抽象

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来源期刊

Journal of Nanoparticle Research 工程技术-材料科学：综合

CiteScore

4.40

自引率

4.00%

发文量

198

审稿时长

3.9 months

期刊介绍： The objective of the Journal of Nanoparticle Research is to disseminate knowledge of the physical, chemical and biological phenomena and processes in structures that have at least one lengthscale ranging from molecular to approximately 100 nm (or submicron in some situations), and exhibit improved and novel properties that are a direct result of their small size. Nanoparticle research is a key component of nanoscience, nanoengineering and nanotechnology. The focus of the Journal is on the specific concepts, properties, phenomena, and processes related to particles, tubes, layers, macromolecules, clusters and other finite structures of the nanoscale size range. Synthesis, assembly, transport, reactivity, and stability of such structures are considered. Development of in-situ and ex-situ instrumentation for characterization of nanoparticles and their interfaces should be based on new principles for probing properties and phenomena not well understood at the nanometer scale. Modeling and simulation may include atom-based quantum mechanics; molecular dynamics; single-particle, multi-body and continuum based models; fractals; other methods suitable for modeling particle synthesis, assembling and interaction processes. Realization and application of systems, structures and devices with novel functions obtained via precursor nanoparticles is emphasized. Approaches may include gas-, liquid-, solid-, and vacuum-based processes, size reduction, chemical- and bio-self assembly. Contributions include utilization of nanoparticle systems for enhancing a phenomenon or process and particle assembling into hierarchical structures, as well as formulation and the administration of drugs. Synergistic approaches originating from different disciplines and technologies, and interaction between the research providers and users in this field, are encouraged.