Vibronic models for nonlinear spectroscopy simulations

Abstract

It is already well established that the high-frequency intramolecular vibrations are responsible for many observed dynamic phenomena in linear and nonlinear electronic spectroscopy such as the spectral lineshape formation, the transition dipole moment, the lifetime borrowing, and vibrational and mixed coherence beats. All these implications together with the vibronic enhancement of the energy and charge transfer can be explained by the vibronic molecular exciton theory and are highly relevant for the description of the spectral dynamics in photosynthetic pigment-protein complexes. In this paper, a few critical points of the vibronic theory application to linear and nonlinear signals are discussed. Models, which differ in the selection and truncation of molecular basis, are compared by analyzing the energy spectrum and exciton-vibrational dynamics in the presence of the energetic disorder. The limits of the widely used one-particle approximation are defined.

Exciton–vibrational coupling in the dynamics and spectroscopy of Frenkel excitons in molecular aggregates

“…A discussion of the implications of reduced models for twodimensional spectroscopy can be found in Ref. [267] …”

Dissipative Exciton Dynamics in Light-Harvesting Complexes

“…Due to its low dimensionality it can be treated numerically rather exactly in comparison to larger aggregates. Hence the dimer is of particular interest as a model system which provides a reference for more complicated systems [20,22,24,26,27,57,[71][72][73][74][75][76][77][78].…”

Effect of an underdamped vibration with both diagonal and off‐diagonal exciton–phonon interactions on excitation energy transfer

“…One of possible origins is the vibronic coherence from the interactions between the exciton and underdamped vibrations as the vibrational frequencies are resonant with the excitonic energy gap, first proposed by Christensson et al From then on, more and more attentions have been paid on the role of these vibrations on the beating signals as well as the corresponding carrier dynamics. It is now accepted that the underdamped vibrations with resonant frequencies may facilitate the EET, charge separation and singlet fission, which have largely extended the knowledge about resonant vibration‐assisted carrier dynamics. Along this way, various fascinating results have been obtained.…”