Quantum coherence is highly involved in photochemical functioning of complex molecular systems. Co-existence and intermixing of electronic and/or vibrational coherences, while never unambiguously identified experimentally, has been proposed to be res
ponsible for this phenomenon. Analysis of multidimensional spectra of a synthetic belt-shaped molecular six-porphyrin nanoring with an inner template clearly shows a great diversity of separable electronic, vibrational and mixed coherences and their cooperation shaping the optical response. The results yield clear assignment of electronic and vibronic states, estimation of excitation transfer rates, and decoherence times. Theoretical considerations prove that the complexity of excitation dynamics and spectral features of the nanoring excitation spectrum is due to combined effect of cyclic symmetry, small geometrical deformations, and vibronic coupling.
The energy transfer processes and coherent phenomena in the fucoxanthin-chlorophyll protein complex, which is responsible for the light harvesting function in marine algae diatoms, were investigated at 77 K by using two-dimensional electronic spectro
scopy. Experiments performed on the femtosecond and picosecond timescales led to separation of spectral dynamics, witnessing evolutions of coherence and population states of the system in the spectral region of ${rm Q}_{y}$ transitions of chlorophylls $a$ and $c$. Analysis of the coherence dynamics allowed us to identify chlorophyll (Chl) $a$ and fucoxanthin intramolecular vibrations dominating over the first few picoseconds. Closer inspection of the spectral region of the ${rm Q}_{y}$ transition of Chl $c$ revealed previously not identified mutually non-interacting chlorophyll $c$ states participating in femtosecond or picosecond energy transfer to the Chl $a$ molecules. Consideration of separated coherent and incoherent dynamics allowed us to hypothesize the vibrations-assisted coherent energy transfer between Chl $c$ and Chl $a$ and the overall spatial arrangement of chlorophyll molecules.
A general theory of electronic excitations in aggregates of molecules coupled to intramolecular vibrations and the harmonic environment is developed for simulation of the third-order nonlinear spectroscopy signals. The model is applied in studies of
the time-resolved two-dimensional coherent spectra of four characteristic model systems: weakly / strongly vibronically coupled molecular dimers coupled to high / low frequency intramolecular vibrations. The results allow us to classify the typical spectroscopic features as well as to define the limiting cases, when the long-lived quantum coherences are present due to vibrational lifetime borrowing, when the complete exciton-vibronic mixing occurs and when separation of excitonic and vibrational coherences is proper.
Coherent dynamics of coupled molecules are effectively characterized by the two-dimensional (2D) electronic coherent spectroscopy. Depending on the coupling between electronic and vibrational states, oscillating signals of purely electronic, purely v
ibrational or mixed origin can be observed. Even in the mixed molecular systems two types of coherent beats having either electronic or vibrational character can be distinguished by analyzing oscillation Fourier maps, constructed from time-resolved 2D spectra. The amplitude of the beatings with the electronic character is heavily affected by the energetic disorder and consequently electronic coherences are quickly dephased. Beatings with the vibrational character depend weakly on the disorder, assuring their long-time survival. We show that detailed modeling of 2D spectroscopy signals of molecular aggregates providesdirect information on the origin of the coherent beatings.
Quantum beats in nonlinear spectroscopy of molecular aggregates are often attributed to electronic phenomena of excitonic systems, while nuclear degrees of freedom are commonly included into models as overdamped oscillations of bath constituents resp
onsible for dephasing. However, molecular systems are coupled to various high-frequency molecular vibrations, which can cause the spectral beats hardly distinguishable from those created by purely electronic coherences. Models containing damped, undamped and overdamped vibrational modes coupled to an electronic molecular transition are discussed in this paper in context of linear absorption and two-dimensional electronic spectroscopy. Analysis of different types of bath models demonstrates how do vibrations map onto two-dimensional spectra and how the damping strength of the coherent vibrational modes can be resolved from spectroscopic signals.
The two-dimensional spectroscopy has recently revealed oscillatory behavior of excitation dynamics in molecular systems. However, in the majority of cases it is strongly debated if excitonic or vibrational wavepackets, or evidences of quantum transpo
rt have been observed. In this letter, the method for distinguishing between vibrational and excitonic wavepacket motion is presented, based on the phase and amplitude relationships of oscillations of distinct peaks, which has been revealed using fundamental analysis of two-dimensional spectrum of two representative systems.
