Theory of the J-band: from the Frenkel exciton to charge transfer
This review concerns the current status of the theory
of formation of the so-called J-band (Jelley, Scheibe, 1936), an
abnormally narrow, high-intensity, red-shifted optical absorption band arising from the aggregation of polymethine dyes.
Two opposite approaches to explaining the physical nature of
the J-band are given special attention. In the first of these, the
old one based on Frenkel’s statistical exciton model, the specific
structure of the dye is considered irrelevant, and the J-band is
explained by assuming that the quickly moving Frenkel exciton
acts to average out the quasistatic disorder in electronic transition energies of molecules in the linear J-aggregate (Knapp,
1984). In the second approach, on the contrary, the specific
structure of the dye (the existence of a quasilinear polymethine
chain ) is supposed to be very important. This new approach is
based on a new theory of charge transfer. The explanation of the
J-band here is that an elementary charge transfer along the
J-aggregate’s chromophore is dynamically pumped by the
chaotic reorganization of nuclei in the nearby environment
at a resonance between electronic and nuclear movements —
when the motion of nuclei being reorganized is only weakly
chaotic (Egorov, 2001).
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