Strongly Coupled Bacteriochlorophyll Dyad Studied Using Two-dimensional Phase-modulated Fluorescence-detected Electronic Spectroscopy

Abstract

Fluorescence-detected two-dimensional electronic spectroscopy (F-2DES) projects the third-order non-linear polarization in a system as an excited electronic state population which is incoherently detected as fluorescence. Multiple variants of F-2DES have been developed. However, none have demonstrated analysis of kinetics and coherences routine in photon-echo 2DES. Here, we report phase-modulated F-2DES measurements on a strongly coupled symmetric bacteriochlorin dyad, a relevant 'toy' model for photosynthetic energy and charge transfer. Coherence map analysis shows that the strongest frequency observed in the dyad is well-separated from the excited state electronic energy gap, and is consistent with a vibrational frequency readily observed in bacteriochlorin monomers. Kinetic rate maps show a picosecond relaxation timescale between the excited states of the dyad. To our knowledge this is the first demonstration of coherence and kinetic analysis using any variant of F-2DES.

arXiv comment14 pages, 7 figures

References in corpus (3)

• Origin of Long Lived Coherences in Light-Harvesting Complexes
• Conformation of self-assembled porphyrin dimers in liposome vesicles by phase-modulation 2D fluorescence spectroscopy
• Incoherent population mixing contributions to phase-modulation two-dimensional coherent excitation spectra

Cited by in corpus (5)

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• Lineshape Analysis of Double-Quantum Multidimensional Coherent Spectra
• Phase-Modulated Rapid-Scanning Fluorescence-Detected Two-Dimensional Electronic Spectroscopy
• Two-dimensional spectroscopy beyond the perturbative limit: the influence of finite pulses and detection modes
• Influence of excitonic coupling, static disorder, and coherent dynamics in action-2D electronic spectroscopy of a molecular dimer model