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The Journal of Physical Chemistry B

Pseudo-Rephasing and Pseudo-Free-Induction-Decay Mechanism in Two-Color Three-Pulse Photon Echo of a Binary System

Hui Dong, Ian Seungwan Ryu, Graham R. Fleming

Published Nov 27, 2013• 1 citation
Publisher

Abstract

We investigate the two-color three-pulse photon echo peak shift in a (left-right) binary system, where each component consists of a heterodimer. On the basis of the model, we find that the effect of the excitonic asymmetry between two components leads to an additional factor in the peak shift. A pseudo-rephasing and pseudo-free-induction-decay mechanism is proposed to explain the resultant negative peak shift, when the differences between the two left/right components have the opposite sign. In such a case, estimates of the electronic coupling strength via two- and one-color peak shift experiments lead to an underestimate of the coupling magnitude.

DOI
10.1021/jp409352z

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We investigate the two-color three-pulse photon echo peak shift in a (left-right) binary system, where each component consists of a heterodimer. On the basis of the model, we find that the effect of the excitonic asymmetry between two components leads to an additional factor in the peak shift. A pseudo-rephasing and pseudo-free-induction-decay mechanism is proposed to explain the resultant negative peak shift, when the differences between the two left/right components have the opposite sign. In such a case, estimates of the electronic coupling strength via two- and one-color peak shift experiments lead to an underestimate of the coupling magnitude.
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A two-color photon echo peak shift measurement to probe the electronic coupling strength in molecular complexes is proposed. Exciton transfer between the electronic eigenstates is neglected and the baths associated with each monomer are assumed to be independent of each other. Within this simplified model, we derive a useful relation which can be used to estimate the electronic coupling strength via a combination of a normal one-color and the present two-color peak shift measurements. A simulation based on the cumulant expansion technique illustrates the validity of our suggestion.
A theoretical description of one- and two-color photon echo peak shifts (PEPS) and two-dimensional (2D) photon echo spectrum (PES) of a coupled chromophore system are presented. The effects of population relaxation in the one-exciton states on both the PEPS and the 2D PES are investigated. For values of time T shorter than the population relaxation time, a finite two-color peak shift magnitude and nonzero cross peaks in the 2D PES provide evidence of electronic coupling between the chromophores. These two distinct observables, i.e., PEPS and off-diagonal peaks, both originate from the electronic coupling. However, it is shown that the PEPS and 2D PES methods can provide complementary information on the structure-dependent nonlinear optical responses of coupled chromophore systems.
In this article the third-order response of an excitonically coupled dimer is studied. The three-pulse photon echo signals were calculated by extracting polarization components from the total polarization in the corresponding phase-matched directions. The total nonlinear response was obtained by numeric propagation of the density matrix, with the exciton-vibrational coupling modeled via Redfield relaxation theory. The full two-dimensional three-pulse photon echo signals and the peak shift were analyzed in terms of the density-matrix dynamics of coherence dephasing and population relaxation. The location of the two-exciton state was found to be essential for proper modeling of the three-pulse photon echo. In particular, an oscillation in the three-pulse photon echo peak shift is found if the two-exciton state is displaced. The oscillations can be related to the dynamics of the one-exciton coherences.
Two-color three pulse photon echo peak shift spectroscopy (2C3PEPS) has been used to probe correlation in electronic transitions in two different regions of the electronic spectrum of a chromophore in the condensed phase. The 2C3PEPS can be done in an “uphill” or a “downhill” sense, where the first two interactions are of lower (higher) frequency than the final interaction with the radiation field. In both cases no correlation between the two spectral regions is observed at very short times. Different parts of the spectrum gain correlation owing to ultrafast solvent motion and the accompanying Stokes shift. We propose a model for the spectral shift that incorporates a conditional probability distribution for transition frequencies in the two spectral regions. The model qualitatively reproduces all the features of complete numerical simulations. Our results show that memory is partially conserved during the spectral diffusion process from the pump to the probe region. The downhill difference peak shift is very sensitive to the time scale of the inertial component of solvation and seems very promising for an accurate determination of this time scale.
The semiconductor Bloch equations are solved numerically for a two-pulse photon-echo configuration. The time-dependent diffracted signal is computed and the significance of many-body effects, carrier relaxation, and dephasing is investigated in detail. Assuming femtosecond-pulse excitation at various intensities and frequencies, distinctly different results are obtained if the exciton or the continuum electron-hole-pair states are excited. It is shown that pure exciton excitation produces a free-induction decay signal and no photon echo. An echo signal is obtained only if continuum states are excited either directly by choosing the central pulse frequencies appropriately or if the band-gap renormalization is sufficiently strong to shift continuum states into resonance. A continuous transition between free-induction decay and photon-echo signal is obtained with increasing excitation amplitude. A perturbative analytical analysis of the equations allows one to identify the role of the many-body effects in producing the different features.