Badry Rania, Elhaes Hanan, Ibrahim Asmaa, Refaat Ahmed, Ibrahim Medhat A
Physics Department, Faculty of Women for Arts, Science and Education, Ain Shams University, Cairo, 11757, Egypt.
Spectroscopy Department, National Research Centre, 33 El-Bohouth St., Dokki, Giza, 12622, Egypt.
Sci Rep. 2024 Nov 6;14(1):27024. doi: 10.1038/s41598-024-72435-7.
Due to its appealing qualities, such as its miniature size and the ability to modify physical properties through chemical synthesis and molecular design, polymer material offers considerable advantages over traditional inorganic material-based electronics. Conjugate polymers are particularly interesting because of their molecular design capabilities, which enable the synthesis of conducting polymers with a variety of ionization potentials and electron affinities (EA), and their ability to control the energy gap and electronegativity (χ). Accordingly, density functional theory (DFT) at the B3LYP/SDD model was used to present possible interactions between polyaniline (PANi) and both alkali and heavy metal oxides. Total dipole moment (TDM), HOMO-LUMO band gap energy (ΔE), ionization energy (IE), EA, chemical hardness (η), chemical potential (μ), electrophilicity index (ω), chemical softness (S), and χ are calculated. TDM of PANi increased while ΔE decreased due to functionalization. The distribution of electronic charge density in molecular electrostatic potential (MESP) maps together with the results of ω reflected the electrophilic nature. The obtained results confirmed that the addition of metal oxides significantly improves the TDM, ΔE, and reactivity descriptors. A strong correlation between the experimental and calculated IR spectra was observed. Additionally, PANi-2MgO and PANi-2MnO model molecules exhibited the highest reactivity. Accordingly, PANi functionalized with MgO and MnO are promising candidates for energy storage devices.
由于聚合物材料具有吸引人的特性，如尺寸微小以及能够通过化学合成和分子设计改变物理性质，因此与传统的基于无机材料的电子产品相比，它具有相当大的优势。共轭聚合物因其分子设计能力而特别引人关注，这种能力使得能够合成具有各种电离势和电子亲和能（EA）的导电聚合物，以及控制能隙和电负性（χ）的能力。因此，采用B3LYP/SDD模型下的密度泛函理论（DFT）来呈现聚苯胺（PANi）与碱金属氧化物和重金属氧化物之间可能的相互作用。计算了总偶极矩（TDM）、HOMO-LUMO带隙能量（ΔE）、电离能（IE）、EA、化学硬度（η）、化学势（μ）、亲电性指数（ω）、化学软度（S）和χ。由于功能化，PANi的TDM增加而ΔE降低。分子静电势（MESP）图中的电子电荷密度分布以及ω的结果反映了亲电性质。所得结果证实，金属氧化物的添加显著改善了TDM、ΔE和反应性描述符。观察到实验红外光谱与计算红外光谱之间有很强的相关性。此外，PANi-2MgO和PANi-2MnO模型分子表现出最高的反应性。因此，用MgO和MnO功能化的PANi是储能器件的有前途的候选材料。
