Lab. de Physique Théorique et Modèles Statistiques, Université Paris-Sud, CNRS, UMR 8626, F-91405 Orsay Cedex, France.
Chem Soc Rev. 2010 Jul;39(7):2453-65. doi: 10.1039/b917724h. Epub 2010 Jun 2.
In this tutorial review, we cover the solid state physics approach to electronic and optical properties of conducting polymers. We attempt to bring together languages and advantages of the solid state theory for polymers and of the quantum chemistry for monomers. We consider polymers as generic one-dimensional semiconductors with features of strongly correlated electronic systems. Our model combines the long range electron-hole Coulomb attraction with a specific effect of strong intra-monomer electronic correlations, which results in effective intra-monomer electron-hole repulsion. Our approach allows to go beyond the single-chain picture and to compare excitons for polymers in solutions and in films. The approach helps connecting such different questions as shallow singlet and deep triplet excitons, stronger binding of interchain excitons in films, crossings of excitons' branches, 1/N energies shifts in oligomers. We describe a strong suppression of the luminescence from free charge carriers by long-range Coulomb interactions. Main attention is devoted to the most requested in applications phenyl based polymers. The specifics of the benzene ring monomer give rise to existence of three possible types of excitons: Wannier-Mott, Frenkel and intermediate ones. We discuss experimental manifestations of various excitons and of their transformations. We touch effects of the time-resolved self-trapping by libron modes leading to formation of torsion polarons.
在本教程综述中,我们介绍了用于研究导电聚合物的电子和光学性质的固态物理方法。我们试图融合聚合物固态理论和单体量子化学的语言和优势。我们将聚合物视为具有强关联电子系统特征的通用一维半导体。我们的模型结合了长程电子-空穴库仑吸引和单体内部电子强关联的特定效应,这导致了单体内部电子-空穴的有效排斥。我们的方法可以超越单链图像,并比较溶液和薄膜中聚合物的激子。该方法有助于连接诸如浅单重态和深三重态激子、薄膜中链间激子更强的结合、激子支的交叉、低聚物中的 1/N 能量移动等不同的问题。我们描述了长程库仑相互作用对自由电荷载流子的发光的强烈抑制。我们主要关注在应用中最需要的苯基聚合物。苯环单体的特殊性导致了三种可能类型激子的存在:Wannier-Mott、Frenkel 和中间型。我们讨论了各种激子及其转化的实验表现。我们还讨论了由 libron 模式引起的时间分辨自陷导致扭转极化子形成的效应。