Disentangling electronic and vibronic coherences in two-dimensional echo spectra

Abstract

The prevalence of long-lasting oscillatory signals in the 2d echo-spectroscopy of light-harvesting complexes has led to a search for possible mechanisms. We investigate how two causes of oscillatory signals are intertwined: (i) electronic coherences supporting delocalized wave-like motion, and (ii) narrow bands in the vibronic spectral density. To disentangle the vibronic and electronic contributions we introduce a time-windowed Fourier transform of the signal amplitude. We find that 2d spectra can be dominated by excitations of pathways which are absent in excitonic energy transport. This leads to an underestimation of the life-time of electronic coherences by 2d spectra.

6 pages, 6 figures

References in corpus (8)

• Environment-Assisted Quantum Walks in Photosynthetic Energy Transfer
• Dephasing assisted transport: Quantum networks and biomolecules
• Environment-Assisted Quantum Transport
• Highly efficient energy excitation transfer in light-harvesting complexes: The fundamental role of noise-assisted transport
• The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae
• Long-Lived Electronic Coherence in Dissipative Exciton-Dynamics of Light-Harvesting Complexes
• High-performance solution of hierarchical equations of motions for studying energy-transfer in light-harvesting complexes
• Exciton-phonon information flow in the energy transfer process of photosynthetic complexes

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