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Issue 28, 2009
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Two-dimensional electronic spectra of an aggregating dye: simultaneous measurement of monomeric and dimeric line-shapes

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Abstract

We present a sequence of two-dimensional electronic spectra of a prototypical cyanine dye, whose spectral properties in aqueous solution are determined by the formation of a monomer–dimer equilibrium. Quantum-chemical methods are utilized to calculate the structure and absorption properties of the two species involved. Our spectroscopic results simultaneously characterize the spectral line-shapes of the two species in terms of underlying dynamic and static disorder, and demonstrate how the two-dimensional technique allows the exploitation of high spectral and temporal resolution in one and the same experiment. The distinctly different spectral relaxation dynamics are quantified in a two-dimensional line-shape analysis, by extracting the time dependent ratios of the diagonal and anti-diagonal peak-widths. Our findings are in line with theoretical considerations, that predict the fluctuational dynamics of an excitonic dimer state to be exchange-narrowed by excitation delocalization.

Graphical abstract: Two-dimensional electronic spectra of an aggregating dye: simultaneous measurement of monomeric and dimeric line-shapes

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Publication details

The article was received on 05 Feb 2009, accepted on 09 Apr 2009 and first published on 18 May 2009


Article type: Paper
DOI: 10.1039/B902477H
Citation: Phys. Chem. Chem. Phys., 2009,11, 5986-5997
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    Two-dimensional electronic spectra of an aggregating dye: simultaneous measurement of monomeric and dimeric line-shapes

    A. Nemeth, V. Lukeš, J. Sperling, F. Milota, H. F. Kauffmann and T. Mančal, Phys. Chem. Chem. Phys., 2009, 11, 5986
    DOI: 10.1039/B902477H

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