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The Journal of Chemical Physics

Two-color three pulse photon echo peak shift spectroscopy

Ritesh Agarwal, Bradley S. Prall, Abbas H. Rizvi, Mino Yang, Graham R. Fleming

Published Apr 8, 2002• 52 citations
Publisher

Abstract

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.

DOI
10.1063/1.1459414

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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 decay of three-pulse photon echo signals from a solute in a liquid solvent is sensitive to the solute’s transition frequency fluctuations, as characterized by its two-point time correlation function, otherwise known as the solvation correlation function. The most widely used method for determining this solvation correlation function from photon echo data involves the three-pulse photon echo peak shift (3PEPS) method. Using this method the long-time decay of the solvation correlation function can be obtained directly, but the determination of the short-time decay requires a difficult numerical fitting procedure. In this study we propose several alternative approaches to determining the solvation correlation function from echo data, the most promising and straightforward of which we call the S3PE (short-time slope of the three-pulse photon echo) method. The accuracy and efficacy of this approach is illustrated by extracting the solvation correlation function from “experimental” data obtained from classical molecular dynamics computer simulations.
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.
The influence of coupling strength and temperature on the solute–solvent interaction of two chromophores in polymer glass is reported. The three-pulse photon echo peak shift method was used to study the dye IR144 in polyvinylformal (PVF) and the dye DTTCI (3,3′-diethylthiatricarbocyanine iodide) in polymethylmethacrylate (PMMA). IR144 is more strongly coupled (larger reorganization energy) to both its intramolecular modes and to the solvent than is DTTCI. Our results can be well described by the linearly coupled harmonic bath model over the range 300 to 30 K. In particular, the strikingly different temperature sensitivities of the long-time (asymptotic) peak shift are well described by the theory. Temperature-independent spectral densities and inhomogeneous widths suffice to quantitatively describe the peak shift data over this temperature range and a number of numerical predictions based on the theoretical model are experimentally confirmed. An ultrafast component corresponding to a decay of ∼100 fs time scale in the transition frequency correlation function is found in all cases, though the amplitude is small for the DTTCI solutions. This ultrafast response is assigned to the inertial response of the solvent. The inertial response measured for DTTCI in PMMA is very similar to our previous measurements of the inertial response for IR144 in PMMA, suggesting that a general characteristic of the solvent is being probed. The weaker coupling of DTTCI produces a drastic increase in the width of the photon echo signal as predicted by theory and strong vibrational quantum beats at 30 K. By contrast, such beats are not observed in the echo signal for IR144.
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.
Optical dephasing of a cyanine dye chromophore in solution is investigated by time-gated photon echo spectroscopy in a three-pulse scattering geometry. The third-order polarization response is gated by up-conversion with a reference pulse in a nonlinear optical crystal. Time gating establishes two controllable periods of system evolution in an optical coherence. The measurements are compared with numerical simulations employing the measured OKE spectrum of solvent (butanol, DMSO) fluctuations. The time-shift of the time-gated echo signals for several gating forming pulse time delays agrees with simulation while the narrower simulated widths suggest a frequency-dependent solute-solvent interaction and the consideration of chromophore vibronic transitions.