An analytical continuation approach for evaluating emission lineshapes of molecular aggregates and the adequacy of multichromophoric Förster theory

Banchi, Leonardo; Costagliola, Gianluca; Ishizaki, Akihito; Giorda, Paolo

doi:10.1063/1.4803694

Cited by 27 publications

(33 citation statements)

References 103 publications

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“…A testimonial to this are recent works attempting to improve their accuracy in various regimes of approximation [40][41][42][43][44][45][46]. Our effort, presented in this work, can be understood as an integral part of this trend.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

Seibt

Mančal

2017

The Journal of Chemical Physics

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We derive equations of motion for the reduced density matrix of a molecular system which undergoes energy transfer dynamics competing with fast internal conversion channels. Environmental degrees of freedom of such a system have no time to relax to quasi-equilibrium in the electronic excited state of the donor molecule, and thus the conditions of validity of Förster and Modified Redfield theories in their standard formulations do not apply. We derive non-equilibrium versions of the two well-known rate theories and apply them to the case of carotenoid-chlorophyll energy transfer. Although our reduced density matrix approach does not account for the formation of vibronic excitons, it still confirms the important role of the donor ground-state vibrational states in establishing the resonance energy transfer conditions. We show that it is essential to work with a theory valid in strong system-bath interaction regime to obtain correct dependence of the rates on donor-acceptor energy gap.

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Section: Introductionmentioning

confidence: 99%

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

Seibt

Mančal

2017

The Journal of Chemical Physics

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“…Second-order corrections to the Boltzmann distribution are widely employed in many perturbative methods 7,10 by replacing t with i β in Eq. (16).…”

Section: Zeroth-order Term G (0)mentioning

confidence: 99%

“…However, in the emission spectrum, the dipole operators are averaged with respect to ρ D e , which is the equilibrium state of the donor's excitons and its bath. The FCE and other 2nd-order methods such as TCL2 10 are not reliable due to the system-bath entanglement.…”

Section: Introductionmentioning

confidence: 99%

“…The MCFT rate can be obtained exactly from numerical methods such as hierarchy equation of motion (HEOM) 3,4 and our recently developed stochastic a) Electronic address: jianshu@mit.edu path integrals (PI). 5,6 However, realistic systems are so large that the exact numerical methods cannot be applied, and thus we need to use perturbative methods such as the full 2nd-order cumulant expansion (FCE), 7 2nd-order time-convolution (TC2), and time-convolution-less (TCL2) [8][9][10] equations. Both the absorption and emission spectra are the Fourier transforms of the time-correlation functions of the dipole operators.…”

Section: Introductionmentioning

confidence: 99%

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Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion

Moix

Cao

2015

The Journal of Chemical Physics

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Articles you may be interested inWe develop a hybrid cumulant expansion method to account for the system-bath entanglement in the emission spectrum in the multi-chromophoric Förster transfer rate. In traditional perturbative treatments, the emission spectrum is usually expanded with respect to the system-bath coupling term in both real and imaginary time. This perturbative treatment gives a reliable absorption spectrum, where the bath is Gaussian and only the real-time expansion is involved. For the emission spectrum, the initial state is an entangled state of the system plus bath. Traditional perturbative methods are problematic when the excitations are delocalized and the energy gap is larger than the thermal energy, since the second-order expansion cannot predict the displacement of the bath. In the present method, the real-time dynamics is carried out by using the 2nd-order cumulant expansion method, while the displacement of the bath is treated more accurately by utilizing the exact reduced density matrix of the system. In a sense, the hybrid cumulant expansion is based on a generalized version of linear response theory with entangled initial states. C 2015 AIP Publishing LLC. [http://dx

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“…There is now an emerging consensus that efficient transport in natural and biologically inspired artificial light-harvesting systems builds on a finely tuned balance of quantum coherence and decoherence caused by environmental noise [9][10][11][12][13], a phenomenon known as environment-assisted quantum transport (ENAQT). This paradigm has emerged with clarity in recent years, as modern spectroscopic techniques first suggested that exciton transport within photosynthetic complexes might be coherent over appreciable time scales [14].…”

Section: Introductionmentioning

confidence: 99%

Global coherence of quantum evolutions based on decoherent histories: Theory and application to photosynthetic quantum energy transport

2016

Self Cite

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Assessing the role of interference in natural and artificial quantum dynamical processes is a crucial task in quantum information theory. To this aim, an appropriate formalism is provided by the decoherent histories framework. While this approach has been deeply explored from different theoretical perspectives, it still lacks of a comprehensive set of tools able to concisely quantify the amount of coherence developed by a given dynamics. In this paper, we introduce and test different measures of the (average) coherence present in dissipative (Markovian) quantum evolutions, at various time scales and for different levels of environmentally induced decoherence. In order to show the effectiveness of the introduced tools, we apply them to a paradigmatic quantum process where the role of coherence is being hotly debated: exciton transport in photosynthetic complexes. To spot out the essential features that may determine the performance of the transport, we focus on a relevant trimeric subunit of the Fenna-Matthews-Olson complex and we use a simplified (Haken-Strobl) model for the system-bath interaction. Our analysis illustrates how the high efficiency of environmentally assisted transport can be traced back to a quantum recoil avoiding effect on the exciton dynamics, that preserves and sustains the benefits of the initial fast quantum delocalization of the exciton over the network. Indeed, for intermediate levels of decoherence, the bath is seen to selectively kill the negative interference between different exciton pathways, while retaining the initial positive one. The concepts and tools here developed show how the decoherent histories approach can be used to quantify the relation between coherence and efficiency in quantum dynamical processes.

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An analytical continuation approach for evaluating emission lineshapes of molecular aggregates and the adequacy of multichromophoric Förster theory

Cited by 27 publications

References 103 publications

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

Ultrafast energy transfer with competing channels: Non-equilibrium Förster and Modified Redfield theories

Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. II. Hybrid cumulant expansion

Global coherence of quantum evolutions based on decoherent histories: Theory and application to photosynthetic quantum energy transport

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