Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

ChemPhysChem

Three‐Pulse Photon‐Echo Peak Shift Spectroscopy and Its Application for the Study of Solvation and Nanoscale Excitons

Megan H. J. Oh, Mayrose R. Salvador, Cathy Y. Wong, Gregory D. Scholes

Published Nov 10, 2010• 13 citations
Publisher

Abstract

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.

DOI
10.1002/cphc.201000712

Related papers

Determining the solvation correlation function from three-pulse photon echoes in liquids

K. F. Everitt, Eitan Geva, James L. Skinner

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.

The Journal of Chemical Physics•Jan 15, 2001•72 citations

The integrated photon echo and solvation dynamics. II. Peak shifts and two-dimensional photon echo of a coupled chromophore system

Minhaeng Cho, Graham R. Fleming

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 Journal of Chemical Physics•Sep 15, 2005•68 citations

Two-color three pulse photon echo peak shift spectroscopy

Ritesh Agarwal, Bradley S. Prall, Abbas H. Rizvi +2 more

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 Journal of Chemical Physics•Apr 8, 2002•52 citations

Three-Pulse Photon Echo Peak Shift Spectroscopy in a Dense Potassium Vapor

Virginia O. Lorenz, Steven T. Cundiff, Shaul Mukamel

The three-pulse photon echo technique has provided significant insight into ultrafast dynamics in a variety of condensed phase systems1. Clear signatures of non-Markovian dynamics in a dense potassium vapor2 provide the opportunity to gain further insight into the correlation function of frequency fluctuations both experimentally and theoretically. Here, experimental three-pulse photon echo peak shifts are compared to calculated peak shifts that include the long-range resonant interactions in a dense atomic vapor within an exciton formalism3. A slow exponential decay in the peak shifts is attributed to long-range resonant interactions.

Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC)•Jun 1, 2007•0 citations

Probing electronic coupling in excitonically coupled heterodimer complexes by two-color three-pulse photon echoes

Tomáš Mančal, Graham R. Fleming

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.

The Journal of Chemical Physics•Nov 16, 2004•27 citations

Two-Color Three Pulse Photon Echo Peak Shift Spectroscopy

Ritesh Agarwal, Bradley S. Prall, Abbas H. Rizvi +2 more

Two-color three pulse photon echo spectroscopy has been used to probe correlation in two different regions of the electronic spectrum of a chromophore in the condensed phase.

International Conference on Ultrafast Phenomena•Jan 1, 2002•0 citations
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.
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.
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 three-pulse photon echo technique has provided significant insight into ultrafast dynamics in a variety of condensed phase systems1. Clear signatures of non-Markovian dynamics in a dense potassium vapor2 provide the opportunity to gain further insight into the correlation function of frequency fluctuations both experimentally and theoretically. Here, experimental three-pulse photon echo peak shifts are compared to calculated peak shifts that include the long-range resonant interactions in a dense atomic vapor within an exciton formalism3. A slow exponential decay in the peak shifts is attributed to long-range resonant interactions.
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.