{"title":"过渡金属配位聚苯胺的计算研究:调整由此产生的混合材料电子特性的第一原理研究","authors":"","doi":"10.1016/j.physb.2024.416597","DOIUrl":null,"url":null,"abstract":"<div><div>Tuning the electronic properties of polyaniline remains one of the most important features for the development of advanced materials in electronics. In this contribution, we use density functional theory to investigate the electronic properties of polyaniline when coordinating transition metals (Mn, Fe, Co, Cu, Zn) are embedded in the polymer structure.</div><div>Importantly, the results reveal that in the presence of transition metal with high electronegativity, the coordinated polyaniline winds up with a decreased gap. Indeed, the band gap for H-PANI decreases from 0.911 eV to 0.513 eV for H-PANI-Mn (lower electronegativity) and to 0.201 eV for H-PANI-Zn (higher electronegativity). This reduction in the energy gap is attributed to enhanced electron delocalization due to increased overlap of electron wavefunctions in the hybrid structure. The results also reveal that the presence of transition metals lead to lower the chemical hardness from 3.252 eV in the case of H-PANI into 0.256 eV for H-PANI-Mn and 0.100 eV for H-PANI-Zn. Additionally, the results from molecular electrostatic potential highlight that PANI-Transition metal sustains more delocalization of charge density distribution compared to H-PANI, leading to molecule polarization which does play a crucial role in various chemical phenomena. These later reveal that the electron density polarization in polyaniline can interestingly be controlled through doping and coordinating the polymer structure with additional transition metals. Therefore, the obtained results might be used in the optimization of electrochemical charge storage in supercapacitors.</div></div>","PeriodicalId":20116,"journal":{"name":"Physica B-condensed Matter","volume":null,"pages":null},"PeriodicalIF":2.8000,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Computational study of transition metal coordinated polyaniline: A first principle investigation into tuning the electronic properties of the resulting hybrid material\",\"authors\":\"\",\"doi\":\"10.1016/j.physb.2024.416597\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Tuning the electronic properties of polyaniline remains one of the most important features for the development of advanced materials in electronics. In this contribution, we use density functional theory to investigate the electronic properties of polyaniline when coordinating transition metals (Mn, Fe, Co, Cu, Zn) are embedded in the polymer structure.</div><div>Importantly, the results reveal that in the presence of transition metal with high electronegativity, the coordinated polyaniline winds up with a decreased gap. Indeed, the band gap for H-PANI decreases from 0.911 eV to 0.513 eV for H-PANI-Mn (lower electronegativity) and to 0.201 eV for H-PANI-Zn (higher electronegativity). This reduction in the energy gap is attributed to enhanced electron delocalization due to increased overlap of electron wavefunctions in the hybrid structure. The results also reveal that the presence of transition metals lead to lower the chemical hardness from 3.252 eV in the case of H-PANI into 0.256 eV for H-PANI-Mn and 0.100 eV for H-PANI-Zn. Additionally, the results from molecular electrostatic potential highlight that PANI-Transition metal sustains more delocalization of charge density distribution compared to H-PANI, leading to molecule polarization which does play a crucial role in various chemical phenomena. These later reveal that the electron density polarization in polyaniline can interestingly be controlled through doping and coordinating the polymer structure with additional transition metals. 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引用次数: 0
摘要
调节聚苯胺的电子特性仍然是开发先进电子材料的最重要特征之一。在这篇论文中,我们利用密度泛函理论研究了在聚合物结构中嵌入配位过渡金属(锰、铁、钴、铜、锌)时聚苯胺的电子特性。重要的是,研究结果表明,当存在电负性较高的过渡金属时,配位聚苯胺的带隙会减小。事实上,H-PANI-Mn(电负性较低)的带隙从 0.911 eV 减小到 0.513 eV,而 H-PANI-Zn(电负性较高)的带隙则减小到 0.201 eV。能隙的减小归因于混合结构中电子波函数重叠的增加导致电子析出的增强。结果还显示,过渡金属的存在导致化学硬度从 H-PANI 的 3.252 eV 降至 H-PANI-Mn 的 0.256 eV 和 H-PANI-Zn 的 0.100 eV。此外,分子静电势的研究结果表明,与 H-PANI 相比,PANI-过渡金属的电荷密度分布更分散,从而导致分子极化,而分子极化在各种化学现象中起着至关重要的作用。这些结果表明,聚苯胺中的电子密度极化可以通过在聚合物结构中掺杂和配位额外的过渡金属来控制。因此,所获得的结果可用于优化超级电容器中的电化学电荷存储。
Computational study of transition metal coordinated polyaniline: A first principle investigation into tuning the electronic properties of the resulting hybrid material
Tuning the electronic properties of polyaniline remains one of the most important features for the development of advanced materials in electronics. In this contribution, we use density functional theory to investigate the electronic properties of polyaniline when coordinating transition metals (Mn, Fe, Co, Cu, Zn) are embedded in the polymer structure.
Importantly, the results reveal that in the presence of transition metal with high electronegativity, the coordinated polyaniline winds up with a decreased gap. Indeed, the band gap for H-PANI decreases from 0.911 eV to 0.513 eV for H-PANI-Mn (lower electronegativity) and to 0.201 eV for H-PANI-Zn (higher electronegativity). This reduction in the energy gap is attributed to enhanced electron delocalization due to increased overlap of electron wavefunctions in the hybrid structure. The results also reveal that the presence of transition metals lead to lower the chemical hardness from 3.252 eV in the case of H-PANI into 0.256 eV for H-PANI-Mn and 0.100 eV for H-PANI-Zn. Additionally, the results from molecular electrostatic potential highlight that PANI-Transition metal sustains more delocalization of charge density distribution compared to H-PANI, leading to molecule polarization which does play a crucial role in various chemical phenomena. These later reveal that the electron density polarization in polyaniline can interestingly be controlled through doping and coordinating the polymer structure with additional transition metals. Therefore, the obtained results might be used in the optimization of electrochemical charge storage in supercapacitors.
期刊介绍:
Physica B: Condensed Matter comprises all condensed matter and material physics that involve theoretical, computational and experimental work.
Papers should contain further developments and a proper discussion on the physics of experimental or theoretical results in one of the following areas:
-Magnetism
-Materials physics
-Nanostructures and nanomaterials
-Optics and optical materials
-Quantum materials
-Semiconductors
-Strongly correlated systems
-Superconductivity
-Surfaces and interfaces