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

The Journal of Chemical Physics

Two-dimensional optical three-pulse photon echo spectroscopy. I. Nonperturbative approach to the calculation of spectra

Tomáš Mančal, Andrei V. Pisliakov, Graham R. Fleming

Published Jun 16, 2006• 74 citations
Publisher

Abstract

The nonperturbative approach to the calculation of nonlinear optical spectra of Seidner et al. [J. Chem. Phys. 103, 3998 (1995)] is extended to describe four-wave mixing experiments. The system-field interaction is treated nonperturbatively in the semiclassical dipole approximation, enabling a calculation of third order nonlinear spectroscopic signals directly from molecular dynamics and an efficient modeling of multilevel systems exhibiting relaxation and transfer phenomena. The method, coupled with the treatment of dynamics within the Bloch model, is illustrated by calculations of the two-dimensional three-pulse photon echo spectra of a simple model system-a two-electronic-level molecule. The nonperturbative calculations reproduce well-known results obtained by perturbative methods. Technical limitations of the nonperturbative approach in dealing with a dynamic inhomogeneity are discussed, and possible solutions are suggested. An application of the approach to an excitonically coupled dimer system with emphasis on the manifestation of complex exciton dynamics in two-dimensional optical spectra is presented in paper II Pisliakov et al. [J. Chem. Phys. 124, 234505 (2006), following paper].

DOI
10.1063/1.2200704

Related papers

Nonperturbative approach to the nonlinear photon echo of V-type system

Xue Zhang, Dong, Hui

The analysis of nonlinear spectroscopy, widely used to study the dynamics and structures of condensed-phase matter, typically employs a perturbative approach noticing the weak interaction between the laser and the matter of interest. However, such perturbative approach is no longer applicable once the interaction between the laser and the matter is strong. We adapt the method of quantum dynamical evolution into the calculation of signal and present the response formalism of the nonlinear spectroscopy in a nonperturbative approach. In this new approach, we demonstrate that in addition to the third-order term in the perturbative method, the higher-order terms have essential contributions to the nonlinear signal of the two-pulse and three-pulse photon echo (2PPE and 3PPE). The detailed calculations are demonstrated with the example of a three-level V-type system, which is widely used in the studies of quantum optics. We consider the effect of the environment via a pure dephasing mechanism with both the localized modes of each molecule and the shared modes between molecules.

arXiv:2206.10857•Jun 22, 2022•0 citations

Nonperturbative approach to the nonlinear photon echo of a V-type system

Xue Zhang, Hui Dong

The analysis of nonlinear spectroscopy, widely used to study the dynamics and structures of condensed-phase matter, typically employs a perturbative approach noticing the weak interaction between the laser and the matter of interest. However, such a perturbative approach is no longer applicable once the interaction between the laser and the matter is strong. We adapt the method of quantum dynamical evolution into the calculation of signal and present the response formalism of the nonlinear spectroscopy in a nonperturbative approach. In this approach, we demonstrate that, in addition to the third-order term in the perturbative method, the higher-order terms have essential contributions to the nonlinear signal of the two-pulse and three-pulse photon echo (2PPE and 3PPE). The detailed calculations are demonstrated with the example of a three-level V-type system, which is widely used in the studies of quantum optics. We consider the effect of the environment via a pure dephasing mechanism with both the localized modes of each molecule and the shared modes between molecules.

Physical Review A•Oct 24, 2022•2 citations

Efficient method for the calculation of time- and frequency-resolved four-wave mixing signals and its application to photon-echo spectroscopy

Maxim F. Gelin, Dassia Egorova, Wolfgang Domcke

An efficient method has been developed for the calculation of third-order time- and frequency-resolved optical signals. To obtain the general four-wave mixing signal, seven auxiliary density matrices have to be propagated in time. For the special cases of two-pulse photon-echo and transient-grating signals, two or three density matrices, respectively, are required. The method is limited to weak laser fields (it is thus valid within the third-order perturbation theory) but allows for any pulse durations and automatically accounts for pulse-overlap effects. To illustrate the method, we present the explicit derivation of the three-pulse photon-echo signal. Any other third-order optical signal can be calculated in the same manner. As an example, two- and three-pulse photon-echo and transient-grating signals for a weakly damped displaced harmonic oscillator have been calculated.

The Journal of Chemical Physics•Oct 22, 2005•93 citations

Two-dimensional electronic spectroscopy of an excitonically coupled dimer

Pär Kjellberg, Ben Brüggemann, Tõnu Pullerits

The two-dimensional three-pulse photon echo signals from a dimer system are investigated in detail. A perturbative approach is used to calculate the response of the system via a numerical propagation of the density matrix in exciton state representation. Exciton vibrational coupling is modeled by Redfield relaxation theory. The main goal of this paper is to dissect the two-dimensional spectrum of the dimer to give better understanding of how the dynamics influence the spectral features. We will show how different Liouville pathways lead to the appearance/disappearance of diagonal and cross peaks. The inclusion of a Gaussian shaped electric field will be contrasted to the use of delta-pulses in the impulsive limit. The impulsive limit is found to be a satisfactory approximation at long population times, while at shorter times, in the pulse-overlap region, more realistic electric fields are called for.

Physical Review B•Jul 26, 2006•115 citations

Four-wave mixing and terahertz emission from three-level systems in quantum wells: Effects of inhomogeneous broadening

Xuejun Zhu, Mark S. Hybertsen, P. B. Littlewood +1 more

Using a perturbation theory based on the density-matrix formulation, we study the nonlinear optical responses of a noninteracting three-level model system to consecutive coherent pulsed excitations, as realized in several recent experiments involving excitonic transitions in quantum wells. The terahertz emission, which is a second-order response, and the four-wave mixing signal, a third-order response, are calculated within the rotating-wave approximation, in the presence of detuning, dephasing, and inhomogeneous broadening. We study the quantum beats in the photon echo from transient four-wave mixing experiments of a three-level system. We find that the temporal profile of the photon echo signal in the four-wave mixing experiments depends very strongly on the amount of inhomogeneous broadening of the energy levels involved. Both the position and the intensity of the peaks exhibit a smooth evolution from strong quantum beats to a conventional photon echo as the inhomogeneous broadening increases. These features from our noninteracting model system are compared with a recent experiment, and found to account for a number of experimental observations.

arXiv:cond-mat/9411118•Physical review. B, Condensed matter•Oct 15, 1994•7 citations

Three-pulse photon echo of an excitonic dimer modeled via Redfield theory

Pär Kjellberg, Tõnu Pullerits

In this article the third-order response of an excitonically coupled dimer is studied. The three-pulse photon echo signals were calculated by extracting polarization components from the total polarization in the corresponding phase-matched directions. The total nonlinear response was obtained by numeric propagation of the density matrix, with the exciton-vibrational coupling modeled via Redfield relaxation theory. The full two-dimensional three-pulse photon echo signals and the peak shift were analyzed in terms of the density-matrix dynamics of coherence dephasing and population relaxation. The location of the two-exciton state was found to be essential for proper modeling of the three-pulse photon echo. In particular, an oscillation in the three-pulse photon echo peak shift is found if the two-exciton state is displaced. The oscillations can be related to the dynamics of the one-exciton coherences.

The Journal of Chemical Physics•Jan 6, 2006•35 citations
The nonperturbative approach to the calculation of nonlinear optical spectra of Seidner et al. [J. Chem. Phys. 103, 3998 (1995)] is extended to describe four-wave mixing experiments. The system-field interaction is treated nonperturbatively in the semiclassical dipole approximation, enabling a calculation of third order nonlinear spectroscopic signals directly from molecular dynamics and an efficient modeling of multilevel systems exhibiting relaxation and transfer phenomena. The method, coupled with the treatment of dynamics within the Bloch model, is illustrated by calculations of the two-dimensional three-pulse photon echo spectra of a simple model system-a two-electronic-level molecule. The nonperturbative calculations reproduce well-known results obtained by perturbative methods. Technical limitations of the nonperturbative approach in dealing with a dynamic inhomogeneity are discussed, and possible solutions are suggested. An application of the approach to an excitonically coupled dimer system with emphasis on the manifestation of complex exciton dynamics in two-dimensional optical spectra is presented in paper II Pisliakov et al. [J. Chem. Phys. 124, 234505 (2006), following paper].
The analysis of nonlinear spectroscopy, widely used to study the dynamics and structures of condensed-phase matter, typically employs a perturbative approach noticing the weak interaction between the laser and the matter of interest. However, such perturbative approach is no longer applicable once the interaction between the laser and the matter is strong. We adapt the method of quantum dynamical evolution into the calculation of signal and present the response formalism of the nonlinear spectroscopy in a nonperturbative approach. In this new approach, we demonstrate that in addition to the third-order term in the perturbative method, the higher-order terms have essential contributions to the nonlinear signal of the two-pulse and three-pulse photon echo (2PPE and 3PPE). The detailed calculations are demonstrated with the example of a three-level V-type system, which is widely used in the studies of quantum optics. We consider the effect of the environment via a pure dephasing mechanism with both the localized modes of each molecule and the shared modes between molecules.
The analysis of nonlinear spectroscopy, widely used to study the dynamics and structures of condensed-phase matter, typically employs a perturbative approach noticing the weak interaction between the laser and the matter of interest. However, such a perturbative approach is no longer applicable once the interaction between the laser and the matter is strong. We adapt the method of quantum dynamical evolution into the calculation of signal and present the response formalism of the nonlinear spectroscopy in a nonperturbative approach. In this approach, we demonstrate that, in addition to the third-order term in the perturbative method, the higher-order terms have essential contributions to the nonlinear signal of the two-pulse and three-pulse photon echo (2PPE and 3PPE). The detailed calculations are demonstrated with the example of a three-level V-type system, which is widely used in the studies of quantum optics. We consider the effect of the environment via a pure dephasing mechanism with both the localized modes of each molecule and the shared modes between molecules.
An efficient method has been developed for the calculation of third-order time- and frequency-resolved optical signals. To obtain the general four-wave mixing signal, seven auxiliary density matrices have to be propagated in time. For the special cases of two-pulse photon-echo and transient-grating signals, two or three density matrices, respectively, are required. The method is limited to weak laser fields (it is thus valid within the third-order perturbation theory) but allows for any pulse durations and automatically accounts for pulse-overlap effects. To illustrate the method, we present the explicit derivation of the three-pulse photon-echo signal. Any other third-order optical signal can be calculated in the same manner. As an example, two- and three-pulse photon-echo and transient-grating signals for a weakly damped displaced harmonic oscillator have been calculated.
The two-dimensional three-pulse photon echo signals from a dimer system are investigated in detail. A perturbative approach is used to calculate the response of the system via a numerical propagation of the density matrix in exciton state representation. Exciton vibrational coupling is modeled by Redfield relaxation theory. The main goal of this paper is to dissect the two-dimensional spectrum of the dimer to give better understanding of how the dynamics influence the spectral features. We will show how different Liouville pathways lead to the appearance/disappearance of diagonal and cross peaks. The inclusion of a Gaussian shaped electric field will be contrasted to the use of delta-pulses in the impulsive limit. The impulsive limit is found to be a satisfactory approximation at long population times, while at shorter times, in the pulse-overlap region, more realistic electric fields are called for.
Using a perturbation theory based on the density-matrix formulation, we study the nonlinear optical responses of a noninteracting three-level model system to consecutive coherent pulsed excitations, as realized in several recent experiments involving excitonic transitions in quantum wells. The terahertz emission, which is a second-order response, and the four-wave mixing signal, a third-order response, are calculated within the rotating-wave approximation, in the presence of detuning, dephasing, and inhomogeneous broadening. We study the quantum beats in the photon echo from transient four-wave mixing experiments of a three-level system. We find that the temporal profile of the photon echo signal in the four-wave mixing experiments depends very strongly on the amount of inhomogeneous broadening of the energy levels involved. Both the position and the intensity of the peaks exhibit a smooth evolution from strong quantum beats to a conventional photon echo as the inhomogeneous broadening increases. These features from our noninteracting model system are compared with a recent experiment, and found to account for a number of experimental observations.
In this article the third-order response of an excitonically coupled dimer is studied. The three-pulse photon echo signals were calculated by extracting polarization components from the total polarization in the corresponding phase-matched directions. The total nonlinear response was obtained by numeric propagation of the density matrix, with the exciton-vibrational coupling modeled via Redfield relaxation theory. The full two-dimensional three-pulse photon echo signals and the peak shift were analyzed in terms of the density-matrix dynamics of coherence dephasing and population relaxation. The location of the two-exciton state was found to be essential for proper modeling of the three-pulse photon echo. In particular, an oscillation in the three-pulse photon echo peak shift is found if the two-exciton state is displaced. The oscillations can be related to the dynamics of the one-exciton coherences.