Chemical Physics Letters, Vol.391, No.4-6, 302-307, 2004
A quantitative analysis of excitonic superhyperchromism in porphyrin J-/H-aggregates
We argue that the mixing between energetically well-separated bands should have a magnified importance in the aggregates exhibiting an excitonic structure with a collective superstate, for which the J-/H-aggregates of porphyrins represent excellent examples. We present a quantitative account of the excitonic intensity borrowing in such systems and reveal a remarkably simple explanation of its enhancement: superhyperchromism is manifested by the mediation of the interband (Q-B) coupling between the two superstates (in Q and B) of such aggregates. The significance of the superhyperchromism is conveyed through its effects on the absorption spectrum of a natural 'porphyrin J-aggregate' - the chlorosome. (C) 2004 Elsevier B.V. All rights reserved.