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The Journal of Chemical Physics

Two-color three-pulse photon echoes as a probe of electronic coupling in molecular complexes

Mino Yang, Graham R. Fleming

Published Feb 8, 1999• 62 citations
Publisher

Abstract

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.

DOI
10.1063/1.477893

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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.
Following the earlier work of Yang et al. [J. Chem. Phys. 110 (1999) 2983] analytical expressions for the downhill and uphill resonant two-color three-pulse photon echo peak shift (2C-3PEPS) of a heterodimer system are derived in the impulsive limit. It is shown how to obtain information about coupling between the components of the dimer from the combined one- and two-color peak shift measurements. Further analytical relations are derived which enable site specific information about the environment of the components, including the relative difference of the inhomogeneity and the difference between the energy-gap correlation functions on the heterodimer sites to be obtained. The simulations show only a very small influence of the laser pulse length on the measured values of coupling coefficient and other relevant quantities suggesting that current 2C-3PEPS measurements can find practical application in directly measuring couplings in excitonically coupled heterodimer complexes.
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.
An understanding of chemical reactivity begins with an understanding of the dynamics involved regarding system-bath interactions. Spectroscopic studies of these interactions in condensed-phase multichromophoric systems are intricate and contain much information. Photon-echo spectroscopy has proven to be a useful tool for probing these interactions. A description of three-pulse photon-echo peak shift spectroscopy (3PEPS)--theory, experiment, and application--for the study of solvation and dynamics of nanoscale excitons is presented. Also, we discuss how two-dimensional photon-echo spectroscopy (2DPE) relates to 3PEPS and show how 3PEPS data can be extracted from 2D photon-echo data.
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.
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.