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

Photon echoes of polyatomic molecules in condensed phases

Yi Jing Yan, Shaul Mukamel

Published Jan 1, 1991• 172 citations
Publisher

Abstract

A theory of optical echo spectroscopies of large polyatomic molecules in condensed phases is developed. Using phase space correlation functions, we examine the interrelationships among the following optical measurements: ordinary photon echo, stimulated photon echo, accumulated photon echo, incoherent accumulated photon echo, and pump–probe absorption. Conditions for the elimination of inhomogeneous broadening in these experiments are specified. A multimode Brownian oscillator model is used to account for high frequency molecular vibrations, as well as solvent modes, and electronic dephasing processes. The effects of quantum beats, spectral diffusion, and homogeneous dephasing on the echo signals are studied and compared in detail with pump–probe and hole burning spectroscopy.

DOI
10.1063/1.460376

Related papers

Impulsive pump-probe and photon-echo spectroscopies of dye molecules in condensed phases

Wayne B. Bosma, Yi Jing Yan, Shaul Mukamel

A theory for impulsive resonant pump-probe and photon-echo spectroscopies of polyatomic dyes in solution is developed. A multimode calculation in which the intramolecular and solvation modes are modeled as Brownian oscillators is presented. Electronic dephasing, the time-dependent Stokes shift, and quantum beats are analyzed.

Physical Review A•Dec 1, 1990•86 citations

The solvent spectral density and vibrational multimode approach to optical dephasing: Two-pulse photon echo response

Tzyy‐Schiuan Yang, Peter Vöhringer, David C. Arnett +1 more

A rigorous theoretical connection between the polarizability spectral density obtained from optical Kerr effect (OKE) measurement with the correlation function describing solvent-induced optical dephasing detected in photon echo measurements is given. The experimentally obtained spectral density has a more reasonable physical basis than model correlation function descriptions of solvent fluctuations. The experimental OKE spectrum is demonstrated to provide a natural description of solvent motions that modulate the chromophore electronic states in the case of weak induced-dipolar interactions. The chromophore optically active vibrational modes are obtained from pump-probe spectra and are employed in the calculation of echo signals. It is found that the fast decays of the two-pulse echo signals result from both solvent and solute intramolecular motions while the echo peak shifts are dominated by the solvent intermolecular modes.

The Journal of Chemical Physics•Nov 15, 1995•63 citations

Theory of nonlinear optical experiments with harmonic oscillators

John T. Fourkas, Hitoshi Kawashima, Keith Adam Nelson

We develop a theory of photon-echo phenomena in harmonic vibrational modes. Although classical harmonic oscillators cannot produce any nonlinear optical signal in the linear response limit, we demonstrate that quantum harmonic oscillators that are coupled to any physically reasonable bath can give rise to novel nonlinear optical behavior, even in the perturbative limit. We show that photon echoes in high-frequency vibrational modes are strongly affected by both population relaxation and pure dephasing. The time dependence of the echo signal is shown to be highly sensitive to the amount of inhomogeneous broadening in the vibrational line. As an example, we develop the simple model of population relaxation resulting from linear coupling to the bath and pure dephasing resulting from quadratic coupling to the bath. Counter to the classical picture, echo signal is present when the only coupling to the bath is linear, but absent when the only coupling is quadratic.

The Journal of Chemical Physics•Sep 15, 1995•68 citations

Anharmonic Electron−Phonon Coupling in Condensed Media: 2. Application to Electronic Dephasing, Hole-Burning, and Photon Echo

Mohamad M. Toutounji

While different expressions of homogeneous linear electronic dipole moment time correlation functions and their respective absorption lineshapes of anharmonic systems were derived and discussed at length in part I [Toutounji, M. J. Phys. Chem. B 2010, in press] of this study, the electronic dephasing (zero-phonon line width), caused by pseudolocal phonons, and vibrational relaxation time scales were treated equally, hence, unphysical. In this study electronic dephasing and vibrational structure are correctly accounted for in harmonic and anharmonic multimode systems. Model calculations are presented. Anharmonic hole-burned spectra are calculated using linear anharmonic absorption lineshapes. An analytical expression of hole-burned absorption line shape in terms of the linear dipole moment time correlation function, leading to a hole-burned absorption line shape expressed in time-domain, is reported. An elementary method is utilized to treat nonlinear spectra in anharmonic molecules. The link between a hole-burned spectrum and a 2-pulse photon echo profile is established by combining the theoretical framework of Mukamel and that of Hays-Small, thereby calculating photon echo signals of anharmonic systems. Model photon echo calculations of a solvable harmonic model and an anharmonic system are reported. Applications to Al-phthaolcyanine tetrasulphonate (APT) in hyperquenched glassy ethanol and special pair bacterial reaction center are presented and discussed in detail.

The Journal of Physical Chemistry C•Nov 3, 2010•13 citations

Theory of photon echoes from interacting impurities in crystals with inhomogeneously broadened absorption spectra

Roger F. Loring, Hans C. Andersen, M. D. Fayer

We present a theory of photon echoes from impurity molecules in mixed crystals that takes into account electronic interactions among impurity molecules and inhomogeneous broadening of the electronic absorption spectrum. The system is modeled as a collection of randomly placed interacting two level systems with a distribution of transition energies. The observable of the echo experiment is expanded in powers of the density of two level systems, and the first two terms of this expansion are calculated. A scaling argument suggests that the density expansion is rapidly convergent for concentrations of experimental interest, and the density expansion is used to construct a Padé approximant. At times comparable to or less than the inverse of the width of the inhomogeneous distribution of resonance frequencies, the time dependence of the signal is determined primarily by the interactions between the impurities and is independent of the inhomogeneous width. At longer times the inhomogeneity becomes significant and the echo signal displays a much weaker time dependence. We examine the effect of different microscopic models of inhomogeneous broadening on the echo observable. We demonstrate that the photon echo experiment can provide a sensitive probe of interactions between impurities in mixed crystals.

The Journal of Chemical Physics•Dec 15, 1984•23 citations

Spectroscopy

Abraham Nitzan

Abstract This chapter focuses on spectroscopic applications of time dependent quantum mechanics focusing on molecular spectroscopy in condensed phases. (1) Molecular spectroscopy in the dressed state picture. (2) Resonance Raman scattering. (3) Resonance energy transfer. (4) Collective excitation and emission. (5) Thermal relaxation and dephasing (the Bloch equations, relaxation of a prepared state, dephasing (decoherence), the absorption lineshape, homogeneous and inhomogeneous broadening, motional narrowing, thermal effects in resonance Raman scattering). (6) A case study: Resonance Raman scattering and fluorescence from Azulene in a Naphthalene matrix. (7) Probing inhomogeneous bands (hole-burning spectroscopy, photon echoes, single-molecule spectroscopy. (8) Optical response functions.

•Jun 14, 2024•0 citations
A theory of optical echo spectroscopies of large polyatomic molecules in condensed phases is developed. Using phase space correlation functions, we examine the interrelationships among the following optical measurements: ordinary photon echo, stimulated photon echo, accumulated photon echo, incoherent accumulated photon echo, and pump–probe absorption. Conditions for the elimination of inhomogeneous broadening in these experiments are specified. A multimode Brownian oscillator model is used to account for high frequency molecular vibrations, as well as solvent modes, and electronic dephasing processes. The effects of quantum beats, spectral diffusion, and homogeneous dephasing on the echo signals are studied and compared in detail with pump–probe and hole burning spectroscopy.
A rigorous theoretical connection between the polarizability spectral density obtained from optical Kerr effect (OKE) measurement with the correlation function describing solvent-induced optical dephasing detected in photon echo measurements is given. The experimentally obtained spectral density has a more reasonable physical basis than model correlation function descriptions of solvent fluctuations. The experimental OKE spectrum is demonstrated to provide a natural description of solvent motions that modulate the chromophore electronic states in the case of weak induced-dipolar interactions. The chromophore optically active vibrational modes are obtained from pump-probe spectra and are employed in the calculation of echo signals. It is found that the fast decays of the two-pulse echo signals result from both solvent and solute intramolecular motions while the echo peak shifts are dominated by the solvent intermolecular modes.
We develop a theory of photon-echo phenomena in harmonic vibrational modes. Although classical harmonic oscillators cannot produce any nonlinear optical signal in the linear response limit, we demonstrate that quantum harmonic oscillators that are coupled to any physically reasonable bath can give rise to novel nonlinear optical behavior, even in the perturbative limit. We show that photon echoes in high-frequency vibrational modes are strongly affected by both population relaxation and pure dephasing. The time dependence of the echo signal is shown to be highly sensitive to the amount of inhomogeneous broadening in the vibrational line. As an example, we develop the simple model of population relaxation resulting from linear coupling to the bath and pure dephasing resulting from quadratic coupling to the bath. Counter to the classical picture, echo signal is present when the only coupling to the bath is linear, but absent when the only coupling is quadratic.
While different expressions of homogeneous linear electronic dipole moment time correlation functions and their respective absorption lineshapes of anharmonic systems were derived and discussed at length in part I [Toutounji, M. J. Phys. Chem. B 2010, in press] of this study, the electronic dephasing (zero-phonon line width), caused by pseudolocal phonons, and vibrational relaxation time scales were treated equally, hence, unphysical. In this study electronic dephasing and vibrational structure are correctly accounted for in harmonic and anharmonic multimode systems. Model calculations are presented. Anharmonic hole-burned spectra are calculated using linear anharmonic absorption lineshapes. An analytical expression of hole-burned absorption line shape in terms of the linear dipole moment time correlation function, leading to a hole-burned absorption line shape expressed in time-domain, is reported. An elementary method is utilized to treat nonlinear spectra in anharmonic molecules. The link between a hole-burned spectrum and a 2-pulse photon echo profile is established by combining the theoretical framework of Mukamel and that of Hays-Small, thereby calculating photon echo signals of anharmonic systems. Model photon echo calculations of a solvable harmonic model and an anharmonic system are reported. Applications to Al-phthaolcyanine tetrasulphonate (APT) in hyperquenched glassy ethanol and special pair bacterial reaction center are presented and discussed in detail.
We present a theory of photon echoes from impurity molecules in mixed crystals that takes into account electronic interactions among impurity molecules and inhomogeneous broadening of the electronic absorption spectrum. The system is modeled as a collection of randomly placed interacting two level systems with a distribution of transition energies. The observable of the echo experiment is expanded in powers of the density of two level systems, and the first two terms of this expansion are calculated. A scaling argument suggests that the density expansion is rapidly convergent for concentrations of experimental interest, and the density expansion is used to construct a Padé approximant. At times comparable to or less than the inverse of the width of the inhomogeneous distribution of resonance frequencies, the time dependence of the signal is determined primarily by the interactions between the impurities and is independent of the inhomogeneous width. At longer times the inhomogeneity becomes significant and the echo signal displays a much weaker time dependence. We examine the effect of different microscopic models of inhomogeneous broadening on the echo observable. We demonstrate that the photon echo experiment can provide a sensitive probe of interactions between impurities in mixed crystals.
Abstract This chapter focuses on spectroscopic applications of time dependent quantum mechanics focusing on molecular spectroscopy in condensed phases. (1) Molecular spectroscopy in the dressed state picture. (2) Resonance Raman scattering. (3) Resonance energy transfer. (4) Collective excitation and emission. (5) Thermal relaxation and dephasing (the Bloch equations, relaxation of a prepared state, dephasing (decoherence), the absorption lineshape, homogeneous and inhomogeneous broadening, motional narrowing, thermal effects in resonance Raman scattering). (6) A case study: Resonance Raman scattering and fluorescence from Azulene in a Naphthalene matrix. (7) Probing inhomogeneous bands (hole-burning spectroscopy, photon echoes, single-molecule spectroscopy. (8) Optical response functions.