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

Physical Review Letters

Time-resolved Femtosecond Photon Echo Probes Bimodal Solvent Dynamics

Maxim S. Pshenichnikov, Koos Duppen, Douwe A. Wiersma

Published Jan 30, 1995• 118 citations
Publisher

Abstract

We report on time-resolved femtosecond photon echo experiments of a dye molecule in a polar solution. The photon echo is time resolved by mixing the echo with a femtosecond gate pulse in a nonlinear crystal. It is shown that the temporal profile of the photon echo allows separation of the homogeneous from the inhomogeneous contribution to the optical spectrum. A biexponential correlation function for frequency fluctuations is used to simulate the echo.

DOI
10.1103/physrevlett.74.674

Related papers

Time-gated photon echo spectroscopy in liquids

Peter Vöhringer, David C. Arnett, Tsung‐Fu Yang +1 more

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.

Chemical Physics Letters•May 1, 1995•103 citations

Optical dephasing on femtosecond time scales: Direct measurement and calculation from solvent spectral densities

Peter Vöhringer, David C. Arnett, R. A. Westervelt +2 more

The connection between dephasing of optical coherence and the measured spectral density of the pure solvent is made through measurements and calculations of photon echo signals. 2-pulse photon echo measurements of a cyanine dye in polar solvents are presented. Signals are recorded for both phase matched directions enabling accurate determination of the echo signal time shift. Echo signals are calculated by two approaches that employ the response function description of nonlinear spectroscopy; (i) a single Brownian oscillator line shape model, and (ii) the line shape obtained using the solvent spectral density. The strongly overdamped Brownian oscillator model incorporates only a single adjustable parameter while the experimental data present two fitting constraints. The second model incorporates the measured solvent spectral density. Both give very good agreement with the experimental results. The significance of the second method lies in this being a new approach to calculate nonlinear spectroscopic signals, for comparison with experimental data, that uses directly the measured spectrum of equilibrium fluctuations of the solvent. This approach also provides a better conceptual perspective for deriving insight into the nature of the solute–solvent coupling mechanism. Comparing the parameters for the strength of interaction in a variety of polar solvents it is found that the coupling involves the solvent polarizability and not the solvent polarity. The interaction mechanism cannot be deduced from the Brownian oscillator calculations.

The Journal of Chemical Physics•Mar 8, 1995•138 citations

New coherent transient technique for femtosecond single-shot homogeneous spectrum measurement

Olavi Ollikainen, Jürgen Gallus, Urs P. Wild +1 more

Summary form only given. Coherent optical transients such as photon echo are a versatile method far measurement of the homogeneous absorption spectrum of molecular systems in the presence of strong inhomogeneous broadening. Such experiments require measurement of the decay of the optical coherence, typically accomplished by gradually varying the time delay between the excitation pulses. Time-domain information is then Fourier transformed to frequency domain by a computer. In this paper we demonstrate a new method that yields the homogeneous spectrum in a single shot of femtosecond laser pulse illumination by performing Fourier transformation of coherent optical transient signal with a lens. We apply this method to measure the homogeneous spectrum of dye molecules in a polymer film in a broad range of temperatures.

Conference on Lasers and Electro-Optics•Nov 27, 2002•0 citations

Time resolved stimulated light scattering from a solvated chromophore: A molecular dynamics study

Alan M. Walsh, Roger F. Loring

We calculate the signal in a time-resolved, coherent light scattering experiment on a dilute solution of a nonpolar solute dissolved in a nonpolar solvent. We model the solute and solvent molecules as electronic two level systems, and assume that only the solute interacts with radiation. The electronic degree of freedom is treated perturbatively within the Born–Oppenheimer approximation. The nuclear degrees of freedom are treated classically, and their effects are modeled by a molecular dynamics simulation. We assume the electronic absorption spectrum is dominated by inhomogeneous broadening. The validity of this assumption for our model is verified through the calculation of the absorption line shape with and without the inhomogeneous broadening assumption. A quantitative measure of the homogeneous dephasing time is obtained from a calculation of the photon echo signal for our model. The time dependence of the light scattering signal is shown to reflect both dynamics of the fluid in its electronic ground state and in its electronic excited state. We analyze the relative importance of contributions to the signal from these two types of dynamics as a function of experimental time scale and laser frequency.

The Journal of Chemical Physics•Jun 15, 1991•21 citations

Femtosecond photon echoes from molecules in solution

P. C. Becker, H. L. Fragnito, J.-Y. Bigot +3 more

Two pulse photon echoes were observed in organic dye molecules in solution using 6-fs optical pulses. The results show an initial rapid dephasing of the echo due to level multiplicity followed by quantum beaks. The temporal decay of the quantum beats is characterized by a ${\mathrm{T}}_{2}$ of about 60 fs.

Physical Review Letters•Jul 31, 1989•231 citations

System−Bath Correlation Function Probed by Conventional and Time-Gated Stimulated Photon Echo

Wim P. de Boeij, Maxim S. Pshenichnikov, Douwe A. Wiersma

We show how in the framework of the multimode Brownian oscillator model the system−bath correlation function can be derived from conventional and time-gated stimulated photon echo experiments and consideration of the linear optical spectra. Experiments are performed on the infrared dye DTTCI in room temperature solutions of ethylene glycol, methanol, and acetonitrile. The obtained correlation function is the sum of several Brownian oscillators, of which four are attributed to intrachromophore vibrational dynamics and the other three to solute−solvent dynamics. The ultrafast part of the correlation function on the time scale of the excitation pulses is interpreted as a free induction decay-like effect due to impulsive excitation of spectrally broad underlying vibrational structure in the dye's electronic transition. The slower parts are assigned to multiple time scale solute−solvent dynamics. The effect of vibrational coherences on the echo measurements is also analyzed; this analysis permits the dissection of the correlation function into a part due to intrachromophore dynamics and a part due to solvation dynamics. The spectral densities associated with these latter oscillators are located in the far infrared, in the same spectral region as probed by the optical Kerr effect. The measurements, however, provide no definite answer to the question of whether these spectral densities are the same.

The Journal of Physical Chemistry•Jan 1, 1996•223 citations
We report on time-resolved femtosecond photon echo experiments of a dye molecule in a polar solution. The photon echo is time resolved by mixing the echo with a femtosecond gate pulse in a nonlinear crystal. It is shown that the temporal profile of the photon echo allows separation of the homogeneous from the inhomogeneous contribution to the optical spectrum. A biexponential correlation function for frequency fluctuations is used to simulate the echo.
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.
The connection between dephasing of optical coherence and the measured spectral density of the pure solvent is made through measurements and calculations of photon echo signals. 2-pulse photon echo measurements of a cyanine dye in polar solvents are presented. Signals are recorded for both phase matched directions enabling accurate determination of the echo signal time shift. Echo signals are calculated by two approaches that employ the response function description of nonlinear spectroscopy; (i) a single Brownian oscillator line shape model, and (ii) the line shape obtained using the solvent spectral density. The strongly overdamped Brownian oscillator model incorporates only a single adjustable parameter while the experimental data present two fitting constraints. The second model incorporates the measured solvent spectral density. Both give very good agreement with the experimental results. The significance of the second method lies in this being a new approach to calculate nonlinear spectroscopic signals, for comparison with experimental data, that uses directly the measured spectrum of equilibrium fluctuations of the solvent. This approach also provides a better conceptual perspective for deriving insight into the nature of the solute–solvent coupling mechanism. Comparing the parameters for the strength of interaction in a variety of polar solvents it is found that the coupling involves the solvent polarizability and not the solvent polarity. The interaction mechanism cannot be deduced from the Brownian oscillator calculations.
Summary form only given. Coherent optical transients such as photon echo are a versatile method far measurement of the homogeneous absorption spectrum of molecular systems in the presence of strong inhomogeneous broadening. Such experiments require measurement of the decay of the optical coherence, typically accomplished by gradually varying the time delay between the excitation pulses. Time-domain information is then Fourier transformed to frequency domain by a computer. In this paper we demonstrate a new method that yields the homogeneous spectrum in a single shot of femtosecond laser pulse illumination by performing Fourier transformation of coherent optical transient signal with a lens. We apply this method to measure the homogeneous spectrum of dye molecules in a polymer film in a broad range of temperatures.
We calculate the signal in a time-resolved, coherent light scattering experiment on a dilute solution of a nonpolar solute dissolved in a nonpolar solvent. We model the solute and solvent molecules as electronic two level systems, and assume that only the solute interacts with radiation. The electronic degree of freedom is treated perturbatively within the Born–Oppenheimer approximation. The nuclear degrees of freedom are treated classically, and their effects are modeled by a molecular dynamics simulation. We assume the electronic absorption spectrum is dominated by inhomogeneous broadening. The validity of this assumption for our model is verified through the calculation of the absorption line shape with and without the inhomogeneous broadening assumption. A quantitative measure of the homogeneous dephasing time is obtained from a calculation of the photon echo signal for our model. The time dependence of the light scattering signal is shown to reflect both dynamics of the fluid in its electronic ground state and in its electronic excited state. We analyze the relative importance of contributions to the signal from these two types of dynamics as a function of experimental time scale and laser frequency.
Two pulse photon echoes were observed in organic dye molecules in solution using 6-fs optical pulses. The results show an initial rapid dephasing of the echo due to level multiplicity followed by quantum beaks. The temporal decay of the quantum beats is characterized by a T2{\mathrm{T}}_{2}T2​ of about 60 fs.
We show how in the framework of the multimode Brownian oscillator model the system−bath correlation function can be derived from conventional and time-gated stimulated photon echo experiments and consideration of the linear optical spectra. Experiments are performed on the infrared dye DTTCI in room temperature solutions of ethylene glycol, methanol, and acetonitrile. The obtained correlation function is the sum of several Brownian oscillators, of which four are attributed to intrachromophore vibrational dynamics and the other three to solute−solvent dynamics. The ultrafast part of the correlation function on the time scale of the excitation pulses is interpreted as a free induction decay-like effect due to impulsive excitation of spectrally broad underlying vibrational structure in the dye's electronic transition. The slower parts are assigned to multiple time scale solute−solvent dynamics. The effect of vibrational coherences on the echo measurements is also analyzed; this analysis permits the dissection of the correlation function into a part due to intrachromophore dynamics and a part due to solvation dynamics. The spectral densities associated with these latter oscillators are located in the far infrared, in the same spectral region as probed by the optical Kerr effect. The measurements, however, provide no definite answer to the question of whether these spectral densities are the same.