Though theoretical treatment of the optical line shapes for polymethine dyes and their aggregates has been a top problem in chemistry and physics for many decades, it has not been solved conclusively to date. The author proposes a novel theory of quantum transitions on the basis of dozy chaos (see [1] and refs there) that gives insight into the nature of the optical line shapes for polymethine dyes, their dimers, H-, H*-, and J-aggregates. This theory formulates a proper definition of electron-nuclear coupling in the dynamics of the transient state, which is of paramount importance for quantum transitions in such organic systems due to their largeness. Dozy chaos is a mix of chaotic motions of the electronic charge, nuclear reorganization and electromagnetic field in the transient state. By dozy chaos the light electrons succeed in controlling the motion of extremely heavy nuclei in the transient state, making it chaotic. Dozy chaos is absent in the initial and final states, and arises in the transient state alone. Formerly in terms of the dozy-chaos theory the author clarified the nature of optical line shapes for dye monomers and J-aggregates. Now this theory is developed to involve exciton effects that are important in dimers and H-aggregates. Some of the results are in theoretical absorption line shapes fitted by the author to the basic experimental data on dye monomers, dimers, H-, H*-, and J-aggregates and also theoretical line shapes fitted to the well-known data on the monomer�dimer and monomer�J-aggregate concentration equilibriums.[1] V.V. Egorov, J. Lumin. 131 (2011) 543.

Optical line shapes for polymethine dyes and their aggregates: Dozy-chaos theory of quantum transitions and its correlation with experiment

243rd National Meeting (2012)

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