Incoherent Energy Transfer Research Articles

Incoherent ultrafast energy transfer in phycocyanin 620 from Thermosynechococcus vulcanus revealed by polarization-controlled two dimensional electronic spectroscopy.

Phycocyanin 620 (PC620) is the outermost light-harvesting complex in phycobilisome of cyanobacteria, engaged in light collection and energy transfer to the core antenna, allophycocyanin. Recently, long-lived exciton-vibrational coherences have been observed in allophycocyanin, accounting for the coherent energy transfer [Zhu et al., Nat. Commun. 15, 3171 (2024)]. PC620 has a nearly identical spatial location of three α84-β84 phycocyanobilin pigment pairs to those in allophycocyanin, inferring an existence of possible coherent energy transfer pathways. However, whether PC620 undergoes coherent or incoherent energy transfer remains debated. Furthermore, accurate determination of energy transfer rates in PC620 is still necessary owing to the spectral overlap and broadening in conventional time-resolved spectroscopic measurements. In this work, the energy transfer process within PC620 was directly resolved by polarization-controlled two dimensional electronic spectroscopy (2DES) and global analysis. The results show that the energy transfer from α84 to the adjacent β84 has a lifetime constant of 400fs, from β155 to β84 of 6-8ps, and from β155 to α84 of 66ps, fully conforming to the Förster resonance energy transfer mechanism. The circular dichroism spectrum also reveals that the α84-β84 pigment pair does not form excitonic dimer, and the observed oscillatory signals are confirmed to be vibrational coherence, excluding the exciton-vibrational coupling. Nodal line slope analysis of 2DES further reveals that all the vibrational modes participate in the energy dissipation of the excited states. Our results consolidate that the ultrafast energy transfer process in PC620 is incoherent, where the twisted conformation of α84 is suggested as the main cause for preventing the formation of α84-β84 excitonic dimer in contrast to allophycocyanin.

J-aggregates and two-dimensional materials indirect-coupling with polariton-assisted resonance energy transfer

Researching resonance energy transfer (RET) from one quantum emitter to another in the strong coupling regime can provide a new route to empower ultrafast quantum manipulations and possess fascinating technological frontiers. However, most of the reports only discussed the weak electronic coupling limit and incoherent energy transfer. Here, we establish a universal theory to investigate RET between two emitters weakly/strongly coupled to a plasmonic mode and analyze the dynamics of RET by utilizing a full-quantum method. Combining with our theory, we investigate the RET rate of a multilayer system in which J-aggregates/monolayer WS2 acts as the donor/acceptor. The calculated results verify that RET rates in the strong coupling regime increase two orders of magnitude compared to the weak coupling regime. Moreover, the coherent energy exchange between two detuned emitters is realized in the strong coupling regime by the time-dependent population calculations. The double Rabi splitting appears in the photoluminescence (PL) spectrum with sufficient RET rates (103ns−1) and coupling strength (g=60 meV). Our work demonstrates a quantitative calculation of RET rates and PL spectrum for the plasmon-biexciton coupled systems, providing a promising way for precise photochemical control, integrated optical device design and quantum information processing.

Fluorescence quenching in aggregates of fucoxanthin–chlorophyll protein complexes: Interplay of fluorescing and dark states

Diatoms, a major group of algae, account for about a quarter of the global primary production on Earth. These photosynthetic organisms face significant challenges due to light intensity variations in their underwater habitat. To avoid photodamage, they have developed very efficient non-photochemical quenching (NPQ) mechanisms. These mechanisms originate in their light-harvesting antenna – the fucoxanthin–chlorophyll protein (FCP) complexes. Spectroscopic studies of NPQ in vivo are often hindered by strongly overlapping signals from the photosystems and their antennae. Fortunately, in vitro FCP aggregates constitute a useful model system to study fluorescence (FL) quenching in diatoms. In this work, we present streak-camera FL measurements on FCPa and FCPb complexes, isolated from a centric diatom Cyclotella meneghiniana, and their aggregates. We find that spectra of non-aggregated FCP are dominated by a single fluorescing species, but the FL spectra of FCP aggregates additionally contain contributions from a redshifted emissive state. We relate this red state to a charge transfer state between chlorophyll c and chlorophyll a molecules. The FL quenching, on the other hand, is due to an additional dark state that involves incoherent energy transfer to the fucoxanthin carotenoids. Overall, the global picture of energy transfer and quenching in FCP aggregates is very similar to that of major light-harvesting complexes in higher plants (LHCII), but microscopic details between FCPs and LHCIIs differ significantly.

Incoherent Energy Transfer between the Baseplate and FMO Protein Explored at Ideal Geometries.

The Förster resonance energy transfer (FRET) between the Fenna-Matthews-Olson (FMO) protein complex and the chlorosomal baseplate (CBP) is investigated by using an idealized model. This simplified model is based on crystal structure and molecular dynamics conformations. Some of the further input, such as the transition dipole moments, was extracted from earlier molecular-level simulations. The resulting model mimics the effects of the relative position between the CBP and the FMO complex on the corresponding FRET efficiency under ideal conditions, involving about 1.3 billion FRET calculations per investigated model. In this idealized model and employing some approximations, it is found that FRET efficiency is almost completely independent of the FMO trimer orientation (displacement, distance, and rotation), despite FMO and CBP being highly structured complexes. Even removing individual FMO BChl triples will only reduce the FRET efficiency by up to 8.6%. An FMO containing only the least efficient BChl triple will retain about 25% of the FRET efficiency of a full FMO complex. In addition to its proposed function as an energetic funnel, FMO is thus identified to act as a highly robust spatial funnel for CBP excitation harvesting, independent of the mutual CBP-FMO orientation.

Fundamental efficiency bound for quantum coherent energy transfer in nanophotonics.

We derive a unified quantum theory of coherent and incoherent energy transfer between two atoms (donor and acceptor) valid in arbitrary Markovian nanophotonic environments. Our theory predicts a fundamental bound η m a x =γ a γ d+γ a for energy transfer efficiency arising from the spontaneous emission rates γd and γa of the donor and acceptor. We propose the control of the acceptor spontaneous emission rate as a new design principle for enhancing energy transfer efficiency. We predict an experiment using mirrors to enhance the efficiency bound by exploiting the dipole orientations of the donor and acceptor. Of fundamental interest, we show that while quantum coherence implies the ultimate efficiency bound has been reached, reaching the ultimate efficiency does not require quantum coherence. Our work paves the way towards nanophotonic analogues of efficiency-enhancing environments known in quantum biological systems.

Insights into Photosynthetic Energy Transfer Gained from Free-Energy Structure: Coherent Transport, Incoherent Hopping, and Vibrational Assistance Revisited.

Giant strides in ultrashort laser pulse technology have enabled real-time observation of dynamical processes in complex molecular systems. Specifically, the discovery of oscillatory transients in the two-dimensional electronic spectra of photosynthetic systems stimulated a number of theoretical investigations exploring the possible physical mechanisms of the remarkable quantum efficiency of light harvesting processes. In this work, we revisit the elementary aspects of environment-induced fluctuations in the involved electronic energies and present a simple way to understand energy flow with the intuitive picture of relaxation in a funnel-type free-energy landscape. The presented free-energy description of energy transfer reveals that typical photosynthetic systems operate in an almost barrierless regime. The approach also provides insights into the distinction between coherent and incoherent energy transfer and the criteria by which the necessity of the vibrational assistance is considered.

Femtosecond excited-state dynamics in chlorosomal carotenoids of the photosynthetic bacterium Chloroflexus aurantiacus revealed by near infrared pump-probe spectroscopy.

In photosynthetic green bacteria, chlorosomes provide light harvesting with high efficiency. Chlorosomal carotenoids (Cars) participate in light harvesting together with the main pigment, bacteriochlorophyll (BChl) c/d/e. In the present work, we studied the excited-state dynamics in Cars from Chloroflexus (Cfx.) aurantiacus chlorosomes by near infrared pump-probe spectroscopy with 25 fs temporal resolution at room temperature. The S2 state of Cars was excited at a wavelength of ∼520 nm, and the absorption changes were probed at 860-1000 nm where the excited state absorption (ESA) of the Cars S2 state occurred. Global analysis of the spectroscopy data revealed an ultrafast (∼15 fs) and large (>130 nm) red shift of the S2 ESA spectrum together with the well-known S2 → S1 IC (∼190 fs) and Cars → BChl c EET (∼120 fs). The S2 lifetime was found to be ∼74 fs. Our findings are in line with earlier results on the excited-state dynamics in Cars in vitro. To explain the extremely fast S2 dynamics, we have tentatively proposed two alternative schemes. The first scheme assumed the formation of a vibrational wavepacket in the S2 state, the motion of which caused a dynamical red shift of the S2 ESA spectrum. The second scheme assumed the presence of two potential minima in the S2 state and incoherent energy transfer between them.

Long-range exciton diffusion in a non-fullerene acceptor: approaching the incoherent limit

Low energetic disorder enables the accurate and high-speed prediction of exciton diffusion parameters in a non-fullerene acceptor.

Quantum dynamics of vibration-assisted excitation energy transfer in phycobiliprotein light-harvesting complex.

Phycobiliprotein is a light-harvesting complex containing linear tetrapyrrole bilin pigments that are responsible for absorption and funneling the sun's energy in cryptophytes algae. In particular, the protein structure determines relative positions and orientations of the pigments and thus controls energy transfer pathways. The present research reveals the impact of molecular vibrations (in the 850-2700 cm-1 region) on excitation energy transfer in phycobiliprotein. The analysis of the excitation energy transfer pathways indicates a possibility of the coherent mechanism of energy transfer (delocalization) in central dihydrobiliverdin pigments and incoherent vibration-assisted energy transfer to peripheral phycocyanobilin pigments at a sub-picosecond time scale. A computational approach that enables modeling the dynamics of the excitation energy transfer with the quantum master equation formalism employing Huang-Rhys factors to describe electronic-vibrational coupling has been developed. The computational methodology has been implemented in PyFREC software.

Quantum dipole emitters in structured environments: a scattering approach: tutorial.

We provide a simple semi-classical formalism to describe the coupling between one or several quantum emitters and a structured environment. Describing the emitter by an electric polarizability, and the surrounding medium by a Green function, we show that an intuitive scattering picture allows one to derive a coupling equation from which the eigenfrequencies of the coupled system can be extracted. The model covers a variety of regimes observed in light-matter interaction, including weak and strong coupling, coherent collective interactions, and incoherent energy transfer. It provides a unified description of many processes, showing that different interaction regimes are actually rooted on the same ground. It can also serve as a basis for the development of more refined models in a full quantum electrodynamics framework.

Signatures of single-photon interaction between two quantum dots located in different cavities of a weakly coupled double microdisk structure

We report on the radiative interaction of two single quantum dots (QDs) each in a separate InP/GaInP-based microdisk cavity via resonant whispering gallery modes. The investigations are based on ab initio coupled disk modes. We apply optical spectroscopy involving a $4f$-setup, as well as mode-selective real space imaging and photoluminescence mapping to discern single QDs coupled to a resonant microdisk mode. Excitation of one disk of the double cavity structure and detecting photoluminescene from the other yields proof of single photon emission of a QD excited by incoherent energy transfer from one disk to the other via a mode in the weak coupling regime. Finally, we present evidence of photons emitted by a QD in one disk that are transferred to the other disk by a resonant mode and are subsequently resonantly scattered by another QD.

Quantum Coherent Excitation Energy Transfer by Carotenoids in Photosynthetic Light Harvesting.

It remains an open question whether quantum coherence and molecular excitons created by delocalization of electronic excited states are essential features of the mechanisms that enable efficient light capture and excitation energy transfer to reaction centers in photosynthetic organisms. The peridinin-chlorophyll a protein from marine dinoflagellates is an example of a light-harvesting system with tightly clustered antenna chromophores in which quantum coherence has long been suspected, but unusually it features the carotenoid peridinin as the principal light absorber for mid-visible photons. We report that broad-band two-dimensional electronic spectroscopy indeed reveals the initial presence of exciton relaxation pathways that enable transfer of excitation from peridinin to chlorophyll a in <20 fs, but the quantum coherence that permits this is very short-lived. Strongly coupled excited-state vibrational distortions of the peridinins trigger a dynamic transition of the electronic structure of the system and a rapid conversion to incoherent energy transfer mechanisms.

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales [Formula: see text]100 fs. Today's understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes.

Coherent and Incoherent Coupling Dynamics between Neutral and Charged Excitons in Monolayer MoSe2

The optical properties of semiconducting transition metal dichalcogenides are dominated by both neutral excitons (electron-hole pairs) and charged excitons (trions) that are stable even at room temperature. While trions directly influence charge transport properties in optoelectronic devices, excitons may be relevant through exciton-trion coupling and conversion phenomena. In this work, we reveal the coherent and incoherent nature of exciton-trion coupling and the relevant time scales in monolayer MoSe2 using optical two-dimensional coherent spectroscopy. Coherent interaction between excitons and trions is definitively identified as quantum beating of cross peaks in the spectra that persists for a few hundred femtoseconds. For longer times up to 10 ps, surprisingly, the relative intensity of the cross peaks increases, which is attributed to incoherent energy transfer likely due to phonon-assisted up-conversion and down-conversion processes that are efficient even at cryogenic temperature.

Quantifying highly efficient incoherent energy transfer in perylene-based multichromophore arrays.

Multichromophore perylene arrays were designed and synthesized to have extremely efficient resonance energy transfer. Using broadband ultrafast photoluminescence and transient absorption spectroscopies, transfer timescales of approximately 1 picosecond were resolved, corresponding to efficiencies of up to 99.98%. The broadband measurements also revealed spectra corresponding to incoherent transfer between localized states. Polarization resolved spectroscopy was used to measure the dipolar angles between donor and acceptor chromophores, thereby enabling geometric factors to be fixed when assessing the validity of Förster theory in this regime. Förster theory was found to predict the correct magnitude of transfer rates, with measured ∼2-fold deviations consistent with the breakdown of the point-dipole approximation at close approach. The materials presented, along with the novel methods for quantifying ultrahigh energy transfer efficiencies, will be valuable for applications demanding extremely efficient energy transfer, including fluorescent solar concentrators, optical gain, and photonic logic devices.

Two-dimensional vibrational-electronic spectroscopy.

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([Fe(III)(CN)6](3-) dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

Correlated quantum dynamics of a single atom collisionally coupled to an ultracold finite bosonic ensemble

We explore the correlated quantum dynamics of a single atom, regarded as an open system, with a spatio-temporally localized coupling to a finite bosonic environment. The single atom, initially prepared in a coherent state of low energy, oscillates in a one-dimensional harmonic trap and thereby periodically penetrates an interacting ensemble of NA bosons held in a displaced trap. We show that the inter-species energy transfer accelerates with increasing NA and becomes less complete at the same time. System-environment correlations prove to be significant except for times when the excess energy distribution among the subsystems is highly imbalanced. These correlations result in incoherent energy transfer processes, which accelerate the early energy donation of the single atom and stochastically favour certain energy transfer channels, depending on the instantaneous direction of transfer. Concerning the subsystem states, the energy transfer is mediated by non-coherent states of the single atom and manifests itself in singlet and doublet excitations in the finite bosonic environment. These comprehensive insights into the non-equilibrium quantum dynamics of an open system are gained by ab initio simulations of the total system with the recently developed multi-layer multi-configuration time-dependent Hartree method for bosons.

Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode

We develop a quantum mechanical formalism to treat the strong coupling between an electromagnetic mode and a vibrational excitation of an ensemble of organic molecules. By employing a Bloch–Redfield–Wangsness approach, we show that the influence of dephasing-type interactions, i.e., elastic collisions with a background bath of phonons, critically depends on the nature of the bath modes. In particular, for long-range phonons corresponding to a common bath, the dynamics of the ‘bright state’ (the collective superposition of molecular vibrations coupling to the cavity mode) is effectively decoupled from other system eigenstates. For the case of independent baths (or short-range phonons), incoherent energy transfer occurs between the bright state and the uncoupled dark states. However, these processes are suppressed when the Rabi splitting is larger than the frequency range of the bath modes, as achieved in a recent experiment (Shalabney et al 2015 Nat. Commun. 6 5981). In both cases, the dynamics can thus be described through a single collective oscillator coupled to a photonic mode, making this system an ideal candidate to explore cavity optomechanics at room temperature.

Partial secular Bloch-Redfield master equation for incoherent excitation of multilevel quantum systems.

We present an efficient theoretical method for calculating the time evolution of the density matrix of a multilevel quantum system weakly interacting with incoherent light. The method combines the Bloch-Redfield theory with a partial secular approximation for one-photon coherences, resulting in a master equation that explicitly exposes the reliance on transition rates and the angles between transition dipole moments in the energy basis. The partial secular Bloch-Redfield master equation allows an unambiguous distinction between the regimes of quantum coherent vs. incoherent energy transfer under incoherent light illumination. The fully incoherent regime is characterized by orthogonal transition dipole moments in the energy basis, leading to a dynamical evolution governed by a coherence-free Pauli-type master equation. The coherent regime requires non-orthogonal transition dipole moments in the energy basis and leads to the generation of noise-induced quantum coherences and population-to-coherence couplings. As a first application, we consider the dynamics of excited state coherences arising under incoherent light excitation from a single ground state and observe population-to-coherence transfer and the formation of non-equilibrium quasisteady states in the regime of small excited state splitting. Analytical expressions derived earlier for the V-type system [T. V. Tscherbul and P. Brumer, Phys. Rev. Lett. 113, 113601 (2014)] are found to provide a nearly quantitative description of multilevel excited-state populations and coherences in both the small- and large-molecule limits.

Theoretical characterization of excitation energy transfer in chlorosome light-harvesting antennae from green sulfur bacteria

We present a theoretical study of excitation dynamics in the chlorosome antenna complex of green photosynthetic bacteria based on a recently proposed model for the molecular assembly. Our model for the excitation energy transfer (EET) throughout the antenna combines a stochastic time propagation of the excitonic wave function with molecular dynamics simulations of the supramolecular structure and electronic structure calculations of the excited states. We characterized the optical properties of the chlorosome with absorption, circular dichroism and fluorescence polarization anisotropy decay spectra. The simulation results for the excitation dynamics reveal a detailed picture of the EET in the chlorosome. Coherent energy transfer is significant only for the first 50fs after the initial excitation, and the wavelike motion of the exciton is completely damped at 100fs. Characteristic time constants of incoherent energy transfer, subsequently, vary from 1ps to several tens of ps. We assign the time scales of the EET to specific physical processes by comparing our results with the data obtained from time-resolved spectroscopy experiments.