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

Femtosecond non-Markovian optical dynamics in solution

Erik T. J. Nibbering, Douwe A. Wiersma, Koos Duppen

Published May 13, 1991• 229 citations
Publisher

Abstract

Femtosecond photon-echo experiments on sodium resorufin in dimethylsulfoxide at room temperature show that optical dephasing in solution is of non-Markovian character. A single Gauss-Markov stochastic modulation process is used to interpret both the femtosecond light-scattering results and the steady-state absorption spectrum. The optical dynamics of this system appears to fall in the intermediate modulation regime. No evidence was found for contributions of slower dynamical processes to the absorption line breadth.

DOI
10.1103/physrevlett.66.2464

Related papers

Non-Markovian correlation effects in time-delayed femtosecond absorption spectroscopy

W. Vogel, D.‐G. Welsch, B. Wilhelmi

The dependence of the electronic absorption spectrum of a dye molecule on the time of delay between the excitation of the molecule by a pump-laser pulse and the probing of the absorption by a test-laser pulse is studied. The effect of dephasing of the molecular transition arising from the interaction with dissipative systems is described by a stochastic modulation of the electronic transition frequency. It is shown that in the case when the two laser pulses are short compared with the correlation time of the frequency modulation and when the spectral linewidth of the pump-laser light is smaller than the bandwidth of the equilibrium absorption spectrum, hole burning appears although the molecules have equal mean transition frequencies. This effect arises from non-Markovian correlations between the dephasings of the molecule during the actions of the pump- and the test-laser pulse. With increasing delay time the holes are smoothed out and disappear when the delay time exceeds the correlation time. Such effects were found in recent femtosecond absorption experiments by Shank et al. [in Ultrafast Phenomena V, dited by G. R. Fleming and A. E. Siegman (Springer, Berlin, 1986), p. 179].

Physical Review A•May 1, 1988•47 citations

Ultrafast optical dephasing in experiments on femtosecond and incoherent photon echo: numerical modeling

V. V. Fedyanin, Каримуллин Камиль Равкатович

Abstract In this paper we develop an approach based on the dynamic theory of optical coherent transients in solids that allows one to describe the processes of ultrafast optical dephasing observed in photon echo spectroscopy in disordered solid-state media. The approach was tested by modeling non-exponential decay curves measured in experiments on femtosecond and incoherent photon echo.

Laser Physics•Oct 25, 2019•7 citations

Homogeneity and Markovity of electronic dephasing in liquid solutions

Being J. Ka, Ming-Liang Zhang, Eitan Geva

The electronic dephasing dynamics of a solvated chromophore is formulated in terms of a non-Markovian master equation. Within this formulation, one describes the effect of the nuclear degrees of freedom on the electronic degrees of freedom in terms of a memory kernel function, which is explicitly dependent on the initial solvent configuration. In the case of homogeneous dynamics, this memory kernel becomes independent of the initial configuration. The Markovity of the dephasing process is also the most conveniently explored by comparing the results obtained via the non-Markovian master equation to these obtained via its Markovian counterpart. The homogeneous memory kernel is calculated for a two-state chromophore in liquid solution, and used to explore the sensitivity of photon echo signals to the heterogeneity and non-Markovity of the underlying solvation dynamics.

The Journal of Chemical Physics•Sep 28, 2006•11 citations

Time-resolved study of ultrafast dephasing processes in solution

A. Kummrow, A. Lau, Kurt Lenz

Electronic dephasing of solutions of all-trans-bis-(dimethylamino)-heptamethinium chloride, its photoisomer, and of 1,${1}^{|\mathrm{I}\mathrm{H}}$,3,3,${3}^{|\mathrm{I}\mathrm{H}}$,${3}^{|\mathrm{I}\mathrm{H}}$-hexamethylindotricarbocyanine iodide (HITCI) is studied using forced light scattering by broad-bandwidth incoherent pump lasers in the wavelength region from 440 to 770 nm. The dephasing slows down as the pump laser wavelength is tuned over the 0-0 transition. Photoisomer and parent heptamethine molecule show comparable behavior in dephasing experiments. Absorption line-shape analysis including resonance Raman experiments indicates a considerable spectral cross relaxation in the absorption band of the parent molecule. The results for HITCI are close to those reported for two-pulse femtosecond photon echoes.

Physical Review A•Mar 1, 1997•7 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

Non-Markovian effects on optical absorption

A. A. Villaeys, J. C. Vallet, S. H. Lin

In this paper, we shall report the investigation of the non-Markovian effects of the dynamical process on optical absorption. It will be shown that in steady-state experiments the non-Markovian effects cannot be probed. The non-Markovian effects on the transient pump-probe experiment are treated, and a couple of typical memory functions have been used to obtain the transient band-shape functions. Finally, probe-pulse duration effects on the absorption are considered.

Physical Review A•May 1, 1991•19 citations
Femtosecond photon-echo experiments on sodium resorufin in dimethylsulfoxide at room temperature show that optical dephasing in solution is of non-Markovian character. A single Gauss-Markov stochastic modulation process is used to interpret both the femtosecond light-scattering results and the steady-state absorption spectrum. The optical dynamics of this system appears to fall in the intermediate modulation regime. No evidence was found for contributions of slower dynamical processes to the absorption line breadth.
The dependence of the electronic absorption spectrum of a dye molecule on the time of delay between the excitation of the molecule by a pump-laser pulse and the probing of the absorption by a test-laser pulse is studied. The effect of dephasing of the molecular transition arising from the interaction with dissipative systems is described by a stochastic modulation of the electronic transition frequency. It is shown that in the case when the two laser pulses are short compared with the correlation time of the frequency modulation and when the spectral linewidth of the pump-laser light is smaller than the bandwidth of the equilibrium absorption spectrum, hole burning appears although the molecules have equal mean transition frequencies. This effect arises from non-Markovian correlations between the dephasings of the molecule during the actions of the pump- and the test-laser pulse. With increasing delay time the holes are smoothed out and disappear when the delay time exceeds the correlation time. Such effects were found in recent femtosecond absorption experiments by Shank et al. [in Ultrafast Phenomena V, dited by G. R. Fleming and A. E. Siegman (Springer, Berlin, 1986), p. 179].
The electronic dephasing dynamics of a solvated chromophore is formulated in terms of a non-Markovian master equation. Within this formulation, one describes the effect of the nuclear degrees of freedom on the electronic degrees of freedom in terms of a memory kernel function, which is explicitly dependent on the initial solvent configuration. In the case of homogeneous dynamics, this memory kernel becomes independent of the initial configuration. The Markovity of the dephasing process is also the most conveniently explored by comparing the results obtained via the non-Markovian master equation to these obtained via its Markovian counterpart. The homogeneous memory kernel is calculated for a two-state chromophore in liquid solution, and used to explore the sensitivity of photon echo signals to the heterogeneity and non-Markovity of the underlying solvation dynamics.
Electronic dephasing of solutions of all-trans-bis-(dimethylamino)-heptamethinium chloride, its photoisomer, and of 1,1∣IH{1}^{|\mathrm{I}\mathrm{H}}1∣IH,3,3,3∣IH{3}^{|\mathrm{I}\mathrm{H}}3∣IH,3∣IH{3}^{|\mathrm{I}\mathrm{H}}3∣IH-hexamethylindotricarbocyanine iodide (HITCI) is studied using forced light scattering by broad-bandwidth incoherent pump lasers in the wavelength region from 440 to 770 nm. The dephasing slows down as the pump laser wavelength is tuned over the 0-0 transition. Photoisomer and parent heptamethine molecule show comparable behavior in dephasing experiments. Absorption line-shape analysis including resonance Raman experiments indicates a considerable spectral cross relaxation in the absorption band of the parent molecule. The results for HITCI are close to those reported for two-pulse femtosecond photon echoes.
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.