On the relation between the echo-peak shift and Brownian-oscillator correlation function

Boeij, W.P. de; Pshenichnikov, Maxim S.; Wiersma, Douwe A.

doi:10.1016/0009-2614(96)00207-2

Cited by 145 publications

(148 citation statements)

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“…The decay of the peak shift from a large initial value to a small or zero final value is therefore closely related to the system-bath correlation function. 49 Book and Scherer have recently demonstrated that by spectrally resolving the photon echo profile information is obtained about dynamics on very fast time scales (<100 fs) that is not apparent from peak shift data. 50 This signal, the frequency-resolved stimulated photon echo (FRSPE, referred to as the wavelength-resolved stimulated photon echo or WRSPE in ref 50), is given by where ω D is the detection frequency of the monochromator.…”

Section: Ultrafast Spectroscopy Of Molecular Aggregatesmentioning

confidence: 99%

Exciton Delocalization and Initial Dephasing Dynamics of Purple Bacterial LH2

et al. 2000

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Ultrafast four-wave mixing spectroscopies are employed to study exciton dynamics associated with the B800 and B850 transitions of LH2 from Rhodobacter sphaeroides. Bacteriochlorophyll a , the constituent chromophore of the B800 and B850 aggregates, is studied as a monomer in solution for comparison. Frequency-resolved pump-probe spectra measured across the B800 and B850 bands establish that at zero delay the transition dipole moment of B850 is substantially larger than that of B800, indicating an initial coherence size of ∼13 chromophores in the (18-member) B850 aggregate. Novel frequency-resolved stimulated photon echo measurements show that intermolecular interactions in the B850 ring reduce the coupling of this band's electronic transition to nuclear motion. In contrast, linear electron-nuclear coupling is comparable in the bacteriochlorophyll a monomer and B800, where exciton coupling is weak. Photon echo peak shift data are consistent with these observations. The initial localization dynamics of the B850 exciton are resolved with transient grating and pump-probe magic angle measurements. These data show that the enhanced transition dipole moment of B850 at the moment of excitation contracts significantly with a time constant of ∼50 fs (for transient grating) due to exciton dephasing resulting in localization. Pump-probe anisotropy measurements reveal substantial transition dipole moment orientational relaxation with nearly the same time constant. These experimental data will be useful for the development of a rigorous theoretical picture of ultrafast exciton dynamics in LH2. B850's large transition dipole moment for absorption may play an important role in the biological function of LH2, as it would enhance the energy transfer rate between B800 and B850.

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Section: Ultrafast Spectroscopy Of Molecular Aggregatesmentioning

confidence: 99%

Exciton Delocalization and Initial Dephasing Dynamics of Purple Bacterial LH2

et al. 2000

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“…In this work we will consider one particular echo observable, the integrated 3PEPS (7,25,48,49). In this experiment one measures the time-integrated intensity…”

Section: ]mentioning

confidence: 99%

Quantum corrections in vibrational and electronic condensed phase spectroscopy: Line shapes and echoes

Lawrence

Skinner

2005

Proc. Natl. Acad. Sci. U.S.A.

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Various linear and nonlinear vibrational and electronic spectroscopy experiments in liquids are usually analyzed within the second-cumulant approximation, and therefore the fundamental quantity of interest is the equilibrium time-correlation function of the fluctuating transition frequency. In the usual approach the ''bath'' variables responsible for the fluctuating frequency are treated classically, leading to a classical time-correlation function. Alternatively, sometimes a quantum correction appropriate for relatively high temperatures is included, which adds an imaginary part to the classical time-correlation function. This approach, although appealing, does not satisfy detailed balance. One can consider a similar correction, but where detailed balance is satisfied, by using the harmonic quantum correction factor. In this article, we compare these approaches for a model system and two realistic examples. Our conclusion is that for linear spectroscopy the classical result is usually adequate, whereas for nonlinear spectroscopy it can be more important to include quantum corrections.dynamics ͉ liquids S pectroscopy is a powerful experimental tool for obtaining information about molecular dynamics in condensed phases, since the frequency at which a molecule absorbs light (be it an electronic or vibrational transition) is perturbed by its local environment, and as this environment changes in time the frequency of the molecule fluctuates accordingly. In the limit that these fluctuations are relatively fast (the homogeneous limit), then one can extract some information about their dynamics by simply measuring the width of the absorption line shape (1, 2). On the other hand, when these frequency fluctuations occur slowly (the inhomogeneous limit), then the line shape contains no dynamical information, and in fact is simply proportional to the distribution of frequencies (2). In this limit experiments such as the three-pulse echo are particularly useful, as they allow one to recover dynamical information absent in the line shape (3). Even within the two-level approximation (the molecule is considered to have only a ground state and a single vibrational or electronic excited state), the interpretation of experiments such as the three-pulse echo is difficult. The theoretical expression that describes the echo response is quite complicated and involves averages of exponentials of integrals of the fluctuating frequency operator (3, 4). To make progress, one typically uses a truncated cumulant expansion (3-5). Although this approximation is uncontrolled [which is sometimes accurate and sometimes not (6-9)], it allows one to express the echo response as a function only of the equilibrium frequency time-correlation function (FTCF). One of the main goals of echo experiments, then, is to extract this FTCF.In general, the FTCF should be calculated quantum mechanically, and as such it is, of course, complex (10). To simplify matters, one often assumes that the system is classical enough that the real part of the quantum FTCF c...

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“…A plot of this shift versus the waiting time t 13 presents the echo shift function. We found in computer simulations 38 and later showed analytically 39 that the echo shift function reflects surprisingly well the correlation function M(t 13 ) and consequently is an excellent probe of the relative amplitudes for the different active vibrational modes. To determine the echo-peak shift, stimulated photon echo signals in conjugated directions: ͑i͒ k 3 ϩk 2 Ϫk 1 and ͑ii͒ k 3 ϩk 1 Ϫk 2 were measured simultaneously.…”

Section: A Optically Active Vibrational Modes Probed By Conventionalmentioning

confidence: 64%

Mode suppression in the non-Markovian limit by time-gated stimulated photon echo

Boeij

Pshenichnikov

Wiersma

1996

The Journal of Chemical Physics

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Mode suppression in the non-Markovian limit by time-gated stimulated photon echo de Boeij, W. P.; Pshenichnikov, M. S.; Wiersma, D. A. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 21-04-2019Mode suppression in the non-Markovian limit by time-gated stimulated photon echo It is demonstrated that enhanced mode suppression in stimulated photon echo experiments can be obtained by diagonal time gating of the echo. This technique is especially important when the optical dynamics of the system is non-Markovian. A two-mode Brownian oscillator model is used to analyze the effect of time gating on the stimulated photon echo. The method is demonstrated on a dye solution of DTTCI in ethylene glycol at room temperature. Experimentally, time gating of the echo is accomplished by means of femtosecond phase-locked heterodyne detected stimulated photon echo. The vibrational dynamics in this system are explored by conventional stimulated photon echo experiments. Especially stimulated photon echo-maximum shift measurements are found to be particularly useful.

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On the relation between the echo-peak shift and Brownian-oscillator correlation function

Cited by 145 publications

References 29 publications

Exciton Delocalization and Initial Dephasing Dynamics of Purple Bacterial LH2

Exciton Delocalization and Initial Dephasing Dynamics of Purple Bacterial LH2

Quantum corrections in vibrational and electronic condensed phase spectroscopy: Line shapes and echoes

Mode suppression in the non-Markovian limit by time-gated stimulated photon echo

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