Abstract
Dozy chaos emerges as a combined effect of the collective chaotic motion of electrons and nuclei, and their chaotic electromagnetic interactions in the transient state of molecules experiencing quantum transitions. Following earlier discussions of the well-known Brönsted relations for proton-transfer reactions; the temperature-dependent electron transfer in Langmuir–Blodgett films; the shape of the optical bands of polymethine dye monomers, their dimers, and J-aggregates, this paper reports one more application of the dozy-chaos theory of molecular quantum transitions. The qualitative and quantitative explanations for shape of a narrow and blue-shifted optical absorption band in H*-aggregates is given on the basis of the dozy-chaos theory by taking into account the dozy-chaos–exciton coupling effect. It is emphasized that in the H*-aggregate chromophore (dimer of cyclic bis-thiacarbocyanines) there is a competition between two Frenkel exciton transitions through the chaotic reorganization motion of nuclear environment. As a result, the highly organized quantum transition to the upper exciton state becomes an exciton-induced source of dozy chaos for the low organized transition to the lower exciton state. This manifests itself in appearing the narrow peak and broad wing in the optical spectrum pattern of H*-aggregates. A similar enhancement in the H*-effect caused by the strengthening of the exciton coupling in H*-dimers, which could be achieved by synthesizing tertiary and quarternary thiacarbocyanine monomers, is predicted.
Highlights
The interest in theoretical studies of the shape of optical bands for aggregates of polymethine dyes has awakened more than 70 years ago in connection with the discovery of the narrow and red-shifted J-band[1] (Fig. 1, left panel) in the experiments carried out by Jelley and Scheibe.[2,3] The theory and computer simulations of the shape of these optical bands have been developed in the last 30 years
Following earlier discussions of the well-known Bronsted relations for proton-transfer reactions; the temperaturedependent electron transfer in Langmuir–Blodgett films; the shape of the optical bands of polymethine dye monomers, their dimers, and J-aggregates, this paper reports one more application of the dozy-chaos theory of molecular quantum transitions
It is emphasized that in the H∗-aggregate chromophore there is a competition between two Frenkel exciton transitions through the chaotic reorganization motion of nuclear environment
Summary
The interest in theoretical studies of the shape of optical bands for aggregates of polymethine dyes has awakened more than 70 years ago in connection with the discovery of the narrow and red-shifted J-band[1] (Fig. 1, left panel) in the experiments carried out by Jelley and Scheibe.[2,3] The theory and computer simulations of the shape of these optical bands have been developed in the last 30 years. The purpose of this paper is to explain the nature of a narrow and blue-shifted optical absorption H∗-band (Fig. 1)
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