聚合物材料的光电性质及杂原子影响微观动力学机制

Due to the fine optoelectronic properties, heteroatoms such as nitrogen and sulfur doped polymers become research focuses in the field of optoelectronics informatics materials. This application indicates to study the optical and electronic properties and the microscopic heteroatoms influence mechanism on the optoelectronics of polymers, Polypyrrole(PPy), Polyaniline (PANi), Poly-p-pyridyl vinylene (PPyV) and Popy-paraphenylene(PPS). The research mainly involves: a fully non-local exchange-correlation formalism within the framework of density functional theory, known as the weighted density approximation (WDA), or local density approximation (LDA) plus U (LDA+U) approach, will be applied to the conjugated polymers, poly-p-phenylene (PPP), poly-para-phenylene vinylenes (PPV) , PPy, PANi, PPS and PPyV for the optical and electronic properties such as polarizability, infrared (IR) and Raman spectra,conductance and dynamical Born effective charges; and we also experimentally determine the IR, Raman spectra and conductance of the materials. The sum frequency generation (SFG), four-wave mixing dual infrared excitation spectrum, binding membrane pressure isotherms and UV-visible absorption spectrum will be employed to study the molecular structure and dynamics of the materials and the interface interested. Then we compare the theoretical and the experimental optical and electrical properties of doped polymers and interested interface of materials PPy,PANi,PPS and PPyV with those of undoped counterparts PPP and PPV. We observe the properties changes, especially the behavior of heteroatoms by using the existing and programmed software. We will explicit the microscopic influence mechanism of the heteroatoms on the optical and electrical properties of the typical polymers. This work has good originality, theoretical importance and application value. It would provide systemic method and tool for the atom or molecule level design and utilization of new polymer materials.

探索具有良好光电性能的聚合物材料已成为光电子信息材料领域的研究热点。本课题拟对几种聚合物PPP，PPV，PANi,PPyV，PPy 和PPS的光电性质和杂原子（氮、硫）对聚合物光电性能微观影响机制进行研究。包括：采用DFT加权密度近似及LDA+U等方法，计算聚合物材料的光电性质包括极化率、红外、Raman谱、电导率、Born有效电荷分布等性质；实验测定聚合物材料的红外、Raman谱和电导率，并利用和频光谱, 结合膜压等温曲线和紫外可见吸收光谱等方法研究材料以及界面分子结构和动力学；从理论和实验两个方面比较含杂原子聚合物（PPy,PANi,PPyV,PPS）及非掺杂聚合物(PPP,PPV)材料光电性质差异、各向异性以及聚合物的态密度和电荷分布规律；观察材料性质变化并特别注意杂原子在其中所起作用；揭示杂原子对聚合物的光电性质的微观影响动力学机制，为新材料的设计及应用提供系统方法和工具。

聚合物由于具有良好的光电性能而成为光电子信息材料领域研究热点。课题研究了杂原子对聚合物的光电性质的微观影响机制，为新材料的设计及应用提供系统方法和工具。应用密度泛函理论，分析研究了基态非简并聚合物的结构特点及结构参数，建立材料性质计算的结构模型，实现聚合物性质的准确预测；研究发现，由于氟原子的强吸电子能力,含氟单体的总能远低于非含氟单体。含氟单体的吸光系数稍大，紫外吸收能量相应增强。酸酐内氧原子的p电子，这一部分电子的局域性比较强，难以转移，HOMO轨道上电子的跃迁不参与可见光吸收。同时对聚合物分子PPP、PPV和PPyV的机构、电学和光学吸收谱进行了研究。.研究表明聚氨酯丙烯酸酯是可以实现的良好的UV固化材料,在聚合期间的聚合物链中由交联结构贡献的良好的热性能，研究表明，有希望合成量子点QD相关的发光材料并具有优异性能的组分拥有低能耗、快干、清洁、高效、分散。使用准谐波Debye模型和混合函数(HSE)来计算GeP型ZnO的热力学、电学和光学性质。寡核苷酸与脂质膜之间的分子相互作用是病毒，适体和各种寡核苷酸基材料功能的关键。本研究利用和频发生振动光谱(SFG-VS)研究了层状阳离子双层膜上寡核苷酸(dT25)的构象变化。构建了门户网站材料模拟设计云科研平台并申请多项相关知识产权。具有重要的科学意义和潜在的应用价值。实现互联网、大数据、云计算等技术，实现对大数据的传输，科研人员的日常管理，科研信息的时时采集，科研进度的精准把控，科研数据的准确分析。发表SCI检索论文20多篇，结合学校研究生教育和双一流建设，培养研究生8名，申请专利12项，其中授权发明专利3项，实用新型专利6项，软件3项。召开同行研讨会8次，邀请著名科学家、院士等来课题组交流和学术会议20多人次；初步建立一支人员结构合理、知识覆盖面广、具有良好团队精神的科研团队。