Normal Mode Analysis of the Spectral Density of the Fenna–Matthews–Olson Light-Harvesting Protein: How the Protein Dissipates the Excess Energy of Excitons

Renger, Thomas; Klinger, Alexander; Steinecker, Florian; Busch, Marcel Schmidt am; Numata, Jorge; Müh, Frank

doi:10.1021/jp3094935

Cited by 110 publications

(200 citation statements)

References 97 publications

(325 reference statements)

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“…These include weak electron-vibration coupling, spatially correlated [49,[53][54][55][56] environmental fluctuations at different chromophores and a slowly relaxing vibrational environment [57]. However, calculations so far indicate that environments at different chromophores are more or less independent [28,58]. The importance of the environment around the chromophores in light-harvesting complexes is indicated by the Stokes shift-the energy difference between the absorption and fluorescence maxima.…”

Section: Energy Transfer and The Question Of Coherencementioning

confidence: 99%

Photosynthetic light harvesting: excitons and coherence

Fassioli

Dinshaw

Arpin

et al. 2014

J. R. Soc. Interface.

262

297

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Photosynthesis begins with light harvesting, where specialized pigmentprotein complexes transform sunlight into electronic excitations delivered to reaction centres to initiate charge separation. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications. We begin by examining the concept of an exciton, an excited electronic state delocalized over several spatially separated molecules, which is the most widely available signature of quantum coherence in light harvesting. We then discuss recent results concerning the possibility that quantum coherence between electronically excited states of donors and acceptors may give rise to a quantum coherent evolution of excitations, modifying the traditional incoherent picture of energy transfer. Key to this (partially) coherent energy transfer appears to be the structure of the environment, in particular the participation of non-equilibrium vibrational modes. We discuss the open questions and controversies regarding quantum coherent energy transfer and how these can be addressed using new experimental techniques.

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Section: Energy Transfer and The Question Of Coherencementioning

confidence: 99%

Photosynthetic light harvesting: excitons and coherence

Fassioli

Dinshaw

Arpin

et al. 2014

J. R. Soc. Interface.

262

297

View full text Add to dashboard Cite

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“…7,59 Comparison between the vibronic coupling matrix elements in Eqs. (38) and (43) shows this rate is a factor of 2 larger for each anticorrelated vibration delocalized over both donor and acceptor pigments than for the corresponding localized pigment vibration. It is instructive to consider the case in which a localized vibration on the donor and a localized vibration on the acceptor are both in near-resonance with the excitonic energy gap but not vibrationally resonant with each other (for example, ω A + δ = ω B − δ ∼ ∆ EX ).…”

Section: Discussionmentioning

confidence: 98%

“…51 In a rigid protein scaffold, fluctuations in the pigment orientations around the equilibrium position are only a small fraction of the center-to-center inter-pigment separations (∼12-15 Å in a FMO monomer 53 or ∼21 Å between bacteriochlorophyll a pigments of adjacent B800 and B850 rings in LH2 54 ) such that the fluctuations in the Coulombic coupling are small compared to the magnitude of the coupling. 38 In this paper, J is approximated as independent of both vibrational coordinates of the protein and intramolecular vibrational coordinates. The above Hamiltonian is standard in describing electronic energy transfer 3 within a network of chromophores which are linearly coupled to vibrational degrees of freedom in their excited states.…”

Section: A Dimer With Intramolecular Environmental and Mixed Vibramentioning

confidence: 99%

“…Protein-pigment binding can change the equilibrium geometry of a pigment in its electronic ground state, 60 and binding site dependent changes in pigment vibrational displacement upon electronic excitation have been reported in computational studies. 38,61 A priori, it seems probable that such a change would also be accompanied by a change in the vibrational frequency. However, a slight difference between pigment vibrational frequencies does not affect the dynamics of the dimer before times on the order of the inverse of the vibrational frequency difference, so it is a useful approximation to consider the effect of chromophore differences in FC displacement alone.…”

Section: Correlated and Anti-correlated Delocalized Vibrationsmentioning

confidence: 99%

“…38 Like an anti-correlated vibration that is delocalized over two pigments, such asymmetric protein modes can simultaneously alter both the average energy of the singly excited states and their energy gap and belong in the nonadiabatic part of the Hamiltonian. Beyond the tuning coordinate analogous to that used in non-adiabatic dynamics, a correlation coordinate is defined to relate decoherence between excitons to the optical and two-photon decoherence processes in 2D spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Tiwari

Jonas

2017

The Journal of Chemical Physics

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Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

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Excited state distribution function for probing Herzberg–Teller vibronic coupling using linear optical response theory: Application to glassy pheophytin a

Toutounji

2021

J Comput Chem

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The goal of the present work is to develop an excited‐state distribution function that can be used to calculate electronic transition dipole moment time correlation functions at a considerably low computational cost. An additional merit of the distribution function is its capability to probe the Hertzberg–Teller vibronic coupling effect in terms of the previously reported Condon correlation functions in the literature without having to start from the equilibrium density operator to probe spectral non‐Condon effects, thereby exploring Hertzberg–Teller vibronic coupling by building on the Condon regime. It is easily extendable to anharmonic systems. Model calculations are reported to show the high degree of accuracy and computational efficiency of the presented approach. Application to a photosynthetic system such as pheophytin a in triethylamine is provided.

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Normal Mode Analysis of the Spectral Density of the Fenna–Matthews–Olson Light-Harvesting Protein: How the Protein Dissipates the Excess Energy of Excitons

Cited by 110 publications

References 97 publications

Photosynthetic light harvesting: excitons and coherence

Photosynthetic light harvesting: excitons and coherence

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Excited state distribution function for probing Herzberg–Teller vibronic coupling using linear optical response theory: Application to glassy pheophytin a

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