Vibronic modulation of lineshapes in two-dimensional electronic spectra

Nemeth, Alexandra; Milota, Franz; Mančal, Tomáš; Lukeš, Vladimı́r; Kauffmann, H. F.; Sperling, Jaroslaw

doi:10.1016/j.cplett.2008.05.057

Cited by 71 publications

(99 citation statements)

References 32 publications

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“…The initial anticorrelation of the site frequencies also explains the absence of quantum beats (with a period of ∼370 fs) in the slope values that are characteristic of coherent excitation of frequency-correlated transitions. 41,24,42,43 As a final test, we computer-generated the frequency trajectories with the same amplitude rms deviations but having strictly Gaussian statistics and uncorrelated site frequencies. Indeed, their substitution instead of those obtained from the genuine MD simulations resulted in identical dynamics for the symmetric and asymmetric modes and the appearance of the quantum beats at ∼350 fs.…”

Section: Resultsmentioning

confidence: 99%

Dissimilar Dynamics of Coupled Water Vibrations

2009

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Dissimilar dynamics of coupled stretch vibrations of a water molecule are revealed by two-dimensional IR correlation spectroscopy. These are caused by essentially non-Gaussian fluctuations of the electric field exerted by the environment on the individual OH stretch vibrations. Non-Gaussian statistics of the individual site frequency fluctuations results in distinctively different dephasing of the symmetric and asymmetric eigenmodes. This phenomenon can only be described if the assumption of Gaussian dynamics in the traditional theories is abandoned.

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Section: Resultsmentioning

confidence: 99%

Dissimilar Dynamics of Coupled Water Vibrations

2009

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“…Experimental situation is typically well described by one or several overdamped Brownian oscillator modes standing for an macroscopic number of harmonic DOF, and several underdamped oscillator modes standing for some important vibrational coordinates, e.g. normal modes of the chromophore molecules [30]. Both of these limits can be conveniently described by by the general Brownian oscillator correlation function C(t) (see [14]) which is a function of temperature T , frequency Ω Bath of the oscillator, damping coefficient γ and the reorganization energy λ.…”

Section: Model System and Block Formalismmentioning

confidence: 99%

“…between so-called coherence time τ and the waiting time T ). The failure to account for this correlation leads sometimes to a complete loss of the experimentally observed dynamics in simulated 2D spectra, such as in the case of the vibrational modulation of electronic 2D spectra [30]. Because vibrational modulation leads to effects similar to those attributed to electronic coherence, developing methods that can account for its effect reliably in complex systems is of utmost importance.…”

Section: Introductionmentioning

confidence: 99%

“…with no energy transfer between the levels) can even be expressed analytically in terms of the socalled energy gap correlation function (EGCF), using the second order cumulant in Magnus expansion [14]. Some examples of small chromophores in solution fall in this category [30,31] when investigated on time scales shorter then radiative life time. For a Gaussian bath this analytical theory is exact, and thus knowing the EGCF of the electronic transitions enables us to determine linear (absorption) as well as non-linear spectra.…”

Section: Introductionmentioning

confidence: 99%

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Parametric projection operator technique for second order non-linear response

Olšina¹,

Mančal²

2012

Chemical Physics

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We demonstrate the application of the recently introduced parametric projector operator technique to a calculation of the second order non-linear optical response of a multilevel molecular system. We derive a parametric quantum master equation (QME) for the time evolution of the excited state of an excitonic system after excitation by the first two pulses in the usual spectroscopic four-wave-mixing scheme. This master equation differs from the usual QME by a correction term which depends on the delay τ between the pulses. In the presence of environmental degrees of freedom with finite bath correlation time and in the presence of intramolecular vibrations we find distinct dynamics of both the excite state populations and the electronic coherence for different delays τ .

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“…The resulting expressions can be easily corrected for the finite bandwidth of the laser [40]. To illustrate how the calculation is done, we consider the ground-state bleach pathway of the rephasing signal (R 3 ).…”

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confidence: 99%

Coherent two-dimensional spectroscopy of a Fano model

Finkelstein-Shapiro¹,

Poulsen²,

Pullerits³

et al. 2016

Phys. Rev. B

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The Fano lineshape arises from the interference of two excitation pathways to reach a continuum. Its generality has resulted in a tremendous success in explaining the lineshapes of many one-dimensional spectroscopies -absorption, emission, scattering, conductance, photofragmentation -applied to very varied systems -atoms, molecules, semiconductors and metals. Unravelling a spectroscopy into a second dimension reveals the relationship between states in addition to decongesting the spectra. Femtosecond-resolved two-dimensional electronic spectroscopy (2DES) is a four-wave mixing technique that measures the time-evolution of the populations, and coherences of excited states. It has been applied extensively to the dynamics of photosynthetic units, and more recently to materials with extended band-structures. In this letter, we solve the full time-dependent third-order response, measured in 2DES, of a Fano model and give the new system parameters that become accessible.Whenever a discrete state and a continuum state interact and radiative transitions are allowed from the ground state to both, an interference occurs that gives rise to the Fano lineshape [1][2][3][4]. In the presence of dissipative processes, it has been shown that the generalized Fano equation consisting of a standard Fano plus a Lorentzian term is [1, 2, 5-9]:where q = µ e /nπV µ c and = (ω L − ω e )/γ e , µ e is the transition dipole moment to the discrete excited state, µ c the transition dipole moment to the continuum, V the coupling of the discrete excited state to the continuum, n the density of states of the continuum, ω e is the energy of the discrete state relative to the ground state, ω L is the radiation field frequency, and γ e = nπV 2 is the linewidth of the excited state, induced by its coupling nV 2 to the continuum set of states. C is the weight of the Lorentzian term and is related to the dissipative processes [6][7][8][9][10]. Since its original inception, the 1961 paper has resulted in more than 8,000 citations testifying to its ubiquity in physics, chemistry and materials science. The first Fano profiles were observed more than 80 years ago in atomic spectra, including photoionization of atoms and photodissociation of small molecules [3,4]. The field of study was established around scattering processes where the phenomena of coupling to a thermal bath resulting in dissipation or decoherence is not important, except in a few cases, notably pressure broadening [11][12][13].The synthesis and control of matter at the nanoscale opened up the observation of Fano profiles to dissipative systems [14][15][16][17][18] which in turn spurred a renewed interest in theoretical descriptions that would solve the problem in open quantum systems [8][9][10][19][20][21], and correctly account for the relaxation. Consequent with this desire to measure dissipation, more sophisticated spectroscopies are to be invoked. 2D electronic spectroscopy (2DES) is arguably one of the best spectroscopies to measure decoherence and relaxation between states [22][23]...

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Vibronic modulation of lineshapes in two-dimensional electronic spectra

Cited by 71 publications

References 32 publications

Dissimilar Dynamics of Coupled Water Vibrations

Dissimilar Dynamics of Coupled Water Vibrations

Parametric projection operator technique for second order non-linear response

Coherent two-dimensional spectroscopy of a Fano model

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