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Title: Nature of the narrow optical band in H*-aggregates: Dozy-chaos–exciton coupling

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{sup *}-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{sup *}-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{sup *}-aggregates. A similar enhancement in the H{sup *}-effect caused by themore » strengthening of the exciton coupling in H{sup *}-dimers, which could be achieved by synthesizing tertiary and quarternary thiacarbocyanine monomers, is predicted.« less
Authors:
 [1]
  1. Photochemistry Center, Russian Academy of Sciences, Moscow, 119421 (Russian Federation)
Publication Date:
OSTI Identifier:
22299868
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Advances; Journal Volume: 4; Journal Issue: 7; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION; COUPLING; ELECTROMAGNETIC INTERACTIONS; FILMS; MONOMERS; PEAKS; PROTONS; SPECTRA; TEMPERATURE DEPENDENCE; TRANSFER REACTIONS