Distinguishing electronic and vibronic coherence in 2D spectra by their temperature dependence

Abstract

Long-lived oscillations in 2D spectra of chlorophylls are at the heart of an ongoing debate. Their physical origin is either a multi-pigment effect, such as excitonic coherence, or primarily stems from localized vibrations. In the present work, we analyze distinguishing characteristics of relative phase difference measured between diagonal- and cross-peak oscillations. While direct discrimination between the two scenarios is obscured when peaks overlap, their sensitivity to temperature provides a stronger argument. We show that vibrational (vibronic) oscillations change relative phase with temperature, while electronic oscillations are only weakly dependent. This highlights that studies of relative phase difference as a function of temperature provide a clear and easily accessible method to distinguish between vibrational and electronic coherences.

15 pages, 5 figures

References in corpus (3)

• Distinctive character of electronic and vibrational coherences in disordered molecular aggregates
• Molecular vibrations-induced quantum beats in two-dimensional electronic spectroscopy
• Disentangling electronic and vibronic coherences in two-dimensional echo spectra

Cited by in corpus (7)

• Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra
• Vibronic coupling explains the ultrafast carotenoid-to-bacteriochlorophyll energy transfer in natural and artificial light harvesters
• Effects of Herzberg--Teller vibronic coupling on coherent excitation energy transfer
• Subtleties of witnessing quantum coherence in non-isolated systems
• Practical Witness for Electronic Coherences
• Simulations of coherent nonlinear optical response of molecular vibronic dimers
• Geometric dependencies of vibronically mediated excitation transfer in rylene dyads