Order–disorder transitions of π‐conjugated polymers in condensed phases. I. General theory
Order–disorder transitions of π‐conjugated polymers in condensed phases. I. General theory
复制标题
π共轭聚合物在凝聚相中的有序-无序转变 I. 一般理论。
DOI：
10.1063/1.451312
复制
发表时间：
1986
影响因子：
4.4
通讯作者：
K. Schweizer
中科院分区：
文献类型：
--
作者：
K. Schweizer
提出了一种新的共轭聚合物在稀溶液和整齐非晶薄膜中有序-无序转换的统计力学理论。单链构型统计和构象依赖的聚合物-溶剂相互作用包括在基本公式中。突变现象是由于聚合物主链的离域电子与周围的可极化溶剂相互作用使棒状构象的能量稳定而产生的。该理论在稀溶液中对π共轭聚合物（多烯和聚二乙炔）进行了详细的发展，并进行了大量的定性和定量预测。现有的实验数据与理论图景一致，并建议进行各种额外的实验来严格检验所提出的想法。统计力学形式被推广到允许分子内氢键，多分散性，溶剂混合物，缺陷相关性和取代基无序。这些效应具有定量结果，但不改变所提出的电子-构象耦合转变的三维溶剂化机制的定性物理。简要讨论了该理论在非晶薄膜中的初步应用。
A novel statistical mechanical theory for the order–disorder transformations of conjugated polymers in dilute solution and neat amorphous films is proposed. Single chain configurational statistics and the conformation‐dependent polymer–solvent interactions are included in the basic formulation. Abrupt transition phenomena arise from the energetic stabilization of the rod‐like conformation via the interaction of the delocalized electrons of the polymer backbone with the surrounding polarizable solvent. The theory is developed in detail for π‐conjugated polymers (polyenes and polydiacetylenes) in dilute solution and makes a significant number of qualitative and quantitative predictions. Available experimental data are consistent with the theoretical picture and a variety of additional experiments are suggested to critically test the proposed ideas. The statistical mechanical formalism is generalized to allow for intramolecular hydrogen bonding, polydispersity, solvent mixtures, defect correlations, and substituent disorder. These effects have quantitative consequences but do not change the qualitative physics of the proposed three‐dimensional solvation mechanism for the coupled electronic‐conformational transitions. Preliminary application of the theory to amorphous films is briefly considered.