Two-dimensional electronic spectroscopy of an excitonically coupled dimer

Kjellberg, P.; Brüggemann, Ben; Pullerits, Tõnu

doi:10.1103/physrevb.74.024303

Cited by 107 publications

(100 citation statements)

References 54 publications

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“…(53) represents a first integral of the EGCF of an underdamped vibrational mode, Eq. (17). The solution of Eq.…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

“…This information is conveniently represented by a 2D plot of the Fourier transformed signal E (3) s (ω t , T, ω τ ) which correlates the absorption frequency ω τ with the frequency ω t of stimulated emission, ground state bleaching and excited state absorption contributions, separated from the absorption event by an adjustable waiting time T . Femtosecond photo-induced evolution of molecular systems is reflected in the amplitude, position and shape of 2D spectral features as functions of the waiting time revealing thus important information about the molecular structure, intramolecular dynamics, as well as the interaction of molecular electronic transitions with their environment [15][16][17].…”

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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“…(53) represents a first integral of the EGCF of an underdamped vibrational mode, Eq. (17). The solution of Eq.…”

Section: Numerical Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Parametric projection operator technique for second order non-linear response

Olšina¹,

Mančal²

2012

Chemical Physics

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“…This laser spectrum somewhat mitigates the prevalence of signals associated with the large transition dipole of state A by only weakly overlapping with that peak, while enhancing the relative contribution of peak B. Through calculations on electronic dimers, Kjellberg and coworkers have demonstrated that at waiting times exceeding the pulse duration, realistic pulse envelopes mostly act as a frequency filter in 2D spectra [36]. Even in the presence of vibronic coupling, the expected effect of the pulse spectrum is mainly the suppression or enhancement of spectral peaks.…”

Section: Two-dimensional Spectroscopymentioning

confidence: 99%

Laser-Limited Signatures of Quantum Coherence

et al. 2015

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The observation of persistent oscillatory signals in multidimensional spectra of proteinpigment complexes has spurred a debate on the role of coherence-assisted electronic energy transfer as a key operating principle in photosynthesis. Vibronic coupling has recently been proposed as an explanation for the long lifetime of the observed spectral beatings. However, photosynthetic systems are inherently complicated, and tractable studies on simple molecular compounds are in demand to fully understand the underlying physics. In this work, we present measurements and calculations on a solvated molecular homodimer with clearly resolvable oscillations in the corresponding twodimensional spectra. Through analysis of the various contributions to the nonlinear response, we succeed in isolating the signal due to inter-exciton coherence. We find that while calculations predict a prolongation of this coherence due to vibronic coupling, the combination of dynamic disorder and vibrational relaxation leads to a coherence decay on a timescale comparable to the electronic dephasing time.

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“…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][24][25]. It is a four-wave mixing technique that gives the full third-order response, from which one can infer the time evolution of the density matrix.…”

mentioning

confidence: 99%

“…The signal is Fourier transformed along the t and τ axes and we obtain 2D correlation maps for fixed time T , also called population time. It has been applied for over a decade to individual chromophores, photosynthetic proteins and even entire cells and has shed light on population transfer and vibronic coherence in natural systems [24,[26][27][28]. More recently, it has been used in structures with extended bands such as colloidal quantum dots, but the framework for simulating the 2D spectra for such systems is still incipient [29][30][31].…”

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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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Two-dimensional electronic spectroscopy of an excitonically coupled dimer

Cited by 107 publications

References 54 publications

Parametric projection operator technique for second order non-linear response

Parametric projection operator technique for second order non-linear response

Laser-Limited Signatures of Quantum Coherence

Coherent two-dimensional spectroscopy of a Fano model

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