Open AccessCorrelated Fluctuations and Intraband Dynamics of J-Aggregates Revealed by Combination of 2DES Schemes
Author(s) -
Luca Bolzonello,
Francesca Fassioli,
Elisabetta Collini
Publication year - 2016
Publication title -
the journal of physical chemistry letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.563
H-Index - 203
ISSN - 1948-7185
DOI - 10.1021/acs.jpclett.6b02433
Subject(s) - exciton , j aggregate , coherence (philosophical gambling strategy) , spectroscopy , chemical physics , relaxation (psychology) , raman spectroscopy , population , redistribution (election) , physics , dynamics (music) , energy transfer , condensed matter physics , materials science , molecular physics , chemistry , quantum mechanics , psychology , social psychology , demography , sociology , politics , political science , acoustics , law
The intraband exciton dynamics of molecular aggregates is a crucial initial step to determine the possibly coherent nature of energy transfer and its implications for the ensuing interband relaxation pathways in strongly coupled excitonic systems. In this work, we fully characterize the intraband dynamics in linear J-aggregates of porphyrins, good model systems for multichromophoric assemblies in biological antenna complexes. Using different 2D electronic spectroscopy schemes together with Raman spectroscopy and theoretical modeling, we provide a full characterization of the inner structure of the main one-exciton band of the porphyrin aggregates. We find that the redistribution of population within the band occurs with a characteristic time of 280 fs and dominates the modulation of an electronic coherence. While we do not find that the coupling to vibrations significantly affects the dynamics of excitonic coherence, our results suggest that exciton fluctuations are nevertheless highly correlated.