Data from: Nature of the optical band shapes in polymethine dyes and H-aggregates: dozy chaos and excitons. Comparison with dimers, H*- and J-aggregates

Results on the theoretical explanation of the shape of optical bands in polymethine dyes, their dimers and aggregates are summarized. The theoretical dependence of the shape of optical bands for the dye monomers in the vinylogous series in line with a change in the solvent polarity is considered. A simple physical (analytical) model of the shape of optical absorption bands in H-aggregates of polymethine dyes is developed based on taking the dozy-chaos dynamics of the transient state and the Frenkel exciton effect in the theory of molecular quantum transitions into account. As an example, the details of the experimental shape of one of the known H-bands are well reproduced by this analytical model under the assumption that the main optical chromophore of H-aggregates is a tetramer resulting from the two most probable processes of inelastic binary collisions in sequence: first, monomers between themselves, and then, between the resulting dimers. The obtained results indicate that in contrast with the compact structure of J-aggregates (brickwork structure), the structure of H-aggregates is not the compact pack-of-cards structure, as stated in the literature, but a loose alternate structure. Based on this theoretical model, a simple general (analytical) method for treating the more complex shapes of optical bands in polymethine dyes in comparison with the H-band under consideration is proposed. This method mirrors the physical process of molecular aggregates forming in liquid solutions: aggregates are generated in the most probable processes of inelastic multiple binary collisions between polymethine species generally differing in complexity. The results obtained are given against a background of the theoretical results on the shape of optical bands in polymethine dyes and their aggregates (dimers, H*- and J-aggregates) previously obtained by V.V.E.

本文总结了聚甲炔染料（polymethine dyes）、其二聚体及聚集体的光学带形状的理论解释相关研究成果。本文探讨了插烯系列（vinylogous series）染料单体的光学带形状随溶剂极性变化的理论依赖关系。基于分子量子跃迁理论中的瞬态惰性混沌（dozy-chaos）动力学与弗伦克尔激子（Frenkel exciton）效应，本文构建了一种简洁的物理解析模型，用于描述聚甲炔染料H聚集体的光吸收带形状。作为示例，在假设H聚集体的主要光学生色团（chromophore）为四聚体，且其形成遵循两种最概然的循序非弹性二元碰撞过程——首先为单体间的碰撞，随后为生成的二聚体间的碰撞——的前提下，该解析模型可精准复现已知H带之一的实验形状细节。研究结果表明，与结构紧凑的J聚集体（砖砌结构（brickwork structure））不同，现有文献中所称的H聚集体并非紧凑的卡片堆叠结构，而是松散的交替排列结构。基于该理论模型，本文提出了一种简便的通用解析方法，用于处理相较于所研究的H带更为复杂的聚甲炔染料光学带形状。该方法契合液态溶液中分子聚集体的形成物理过程：聚集体由复杂度各异的聚甲炔物种间最概然的多步非弹性二元碰撞过程生成。本文所得研究结果，均以V.V.E.此前针对聚甲炔染料及其聚集体（二聚体、H*-聚集体与J聚集体）的光学带形状所取得的理论研究成果为参照背景。