Quantum Coherent Energy Transfer Research Articles

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.

Role of Spatially Correlated Fluctuations in Photosynthetic Excitation Energy Transfer with an Equilibrium and a Nonequilibrium Initial Bath.

The transfer of excitation energy in photosynthetic light-harvesting complexes has inspired growing interest for its scientific and engineering significance. Recent experimental findings have suggested that spatially correlated environmental fluctuations may account for the existence of long-lived quantum coherent energy transfer observed even at physiological temperature. In this paper, we investigate the effects of spatial correlations on the excitation energy transfer dynamics by including a nonequilibrium initial bath in a simulated donor-acceptor model. The initial bath state, which is assumed to be either equilibrium or nonequilibrium, is expanded in powers of coupling strength within the polaron formalism of a quantum master equation. The spatial correlations of bath fluctuations strongly influence the decay of coherence in the dynamics. The role of a nonequilibrium initial bath is also influenced by spatial correlations and becomes the most conspicuous for certain degrees of spatial correlations from which we propose a picture that the spatial correlations of bath fluctuations open up new energy transfer pathways, playing a role of protecting coherence. Besides, we apply the polaron master equation approach to study the dynamics in a two-site subsystem of the FMO complex and provide a practical example that shows the versatility of this approach.

Quantum transport in the FMO photosynthetic light-harvesting complex.

The very high light-harvesting efficiency of natural photosynthetic systems in conjunction with recent experiments, which showed quantum-coherent energy transfer in photosynthetic complexes, raised questions regarding the presence of non-trivial quantum effects in photosynthesis. Grover quantum search, quantum walks, and entanglement have been investigated as possible effects that lead to this efficiency. Here we explain the near-unit photosynthetic efficiency without invoking non-trivial quantum effects. Instead, we use non-equilibrium Green's functions, a mesoscopic method used to study transport in nano-conductors to compute the transmission function of the Fenna-Matthews-Olson (FMO) complex using an experimentally derived exciton Hamiltonian. The chlorosome antenna and the reaction center play the role of input and output contacts, connected to the FMO complex. We show that there are two channels for which the transmission is almost unity. Our analysis also revealed a dephasing-driven regulation mechanism that maintains the efficiency in the presence of varying dephasing potentials.

Effect of Pulse Shaping on Observing Coherent Energy Transfer in Single Light-Harvesting Complexes

Recent experimental and theoretical studies have revealed that quantum coherence plays an important role in the excitation energy transfer in photosynthetic light-harvesting (LH) complexes. Inspired by the recent single-molecule two-color double-pump experiment, we theoretically investigate the effect of pulse shaping on observing coherent energy transfer in the single bacterial LH2 complex. It is found that quantum coherent energy transfer can be observed when the time delay and phase difference between the two laser pulses are controlled independently. However, when the two-color pulses are generated using the pulse-shaping method, how the laser pulses are prepared is crucial to the observation of quantum coherent energy transfer in single photosynthetic complexes.

The feasibility of coherent energy transfer in microtubules.

It was once purported that biological systems were far too 'warm and wet' to support quantum phenomena mainly owing to thermal effects disrupting quantum coherence. However, recent experimental results and theoretical analyses have shown that thermal energy may assist, rather than disrupt, quantum coherent transport, especially in the 'dry' hydrophobic interiors of biomolecules. Specifically, evidence has been accumulating for the necessary involvement of quantum coherent energy transfer between uniquely arranged chromophores in light harvesting photosynthetic complexes. The 'tubulin' subunit proteins, which comprise microtubules, also possess a distinct architecture of chromophores, namely aromatic amino acids, including tryptophan. The geometry and dipolar properties of these aromatics are similar to those found in photosynthetic units indicating that tubulin may support coherent energy transfer. Tubulin aggregated into microtubule geometric lattices may support such energy transfer, which could be important for biological signalling and communication essential to living processes. Here, we perform a computational investigation of energy transfer between chromophoric amino acids in tubulin via dipole excitations coupled to the surrounding thermal environment. We present the spatial structure and energetic properties of the tryptophan residues in the microtubule constituent protein tubulin. Plausibility arguments for the conditions favouring a quantum mechanism of signal propagation along a microtubule are provided. Overall, we find that coherent energy transfer in tubulin and microtubules is biologically feasible.

Photosynthetic light harvesting: excitons and coherence.

Photosynthesis begins with light harvesting, where specialized pigment-protein 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.

Quantum Coherent Energy Transfer over Varying Pathways in Single Light-Harvesting Complexes

The initial steps of photosynthesis comprise the absorption of sunlight by pigment-protein antenna complexes followed by rapid and highly efficient funneling of excitation energy to a reaction center. In these transport processes, signatures of unexpectedly long-lived coherences have emerged in two-dimensional ensemble spectra of various light-harvesting complexes. Here, we demonstrate ultrafast quantum coherent energy transfer within individual antenna complexes of a purple bacterium under physiological conditions. We find that quantum coherences between electronically coupled energy eigenstates persist at least 400 femtoseconds and that distinct energy-transfer pathways that change with time can be identified in each complex. Our data suggest that long-lived quantum coherence renders energy transfer in photosynthetic systems robust in the presence of disorder, which is a prerequisite for efficient light harvesting.

Quantum-coherent energy transfer: implications for biology and new energy technologies

The important thing in science is not so much to obtain new facts as to discover new ways of thinking about them. Sir William Henry Bragg Nobel Prize For Physics, 1915 There is a growing body of scientific evidence that light-initiated reactions in the molecular components of photosynthetic

Robert Silbey 1940–2011

![Graphic][1] The Royal Society Theo Murphy International Scientific Meeting Quantum-coherent energy transfer: implications for biology and new energy technologies was one of the last scientific meetings attended by Bob Silbey, who died on 27 October 2011. As always, he brought his

Quantum Coherence in Photosynthetic Exciton Dynamics

We present numerically exact results for the electronic energy transfer dynamics in the Fenna-Matthews-Olson (FMO) molecular aggregate. In particular, we determine its single excitation subspace dynamics within an open quantum dynamics approach which is based on parameters for the dipolar couplings, site energies and their respective fluctuations. We study and compare the dynamics for parameters according to several models available in the literature. Depending on the model used we find quantum coherent dynamics with coherence times exceeding experimentally observed times but also shorter times for other models. Even strongly overdamped decay of the site populations with no coherent population dynamics is observed for model parameters based on atomistic molecular dynamics. Thus, theoretical understanding at the present stage can neither support nor rule out a picture of quantum coherent energy transfer in natural photosynthesis.

Excitonic energy transfer in light-harvesting complexes in purple bacteria

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has been largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.

Exciton transfer dynamics and quantumness of energy transfer in the Fenna-Matthews-Olson complex

We present numerically exact results for the quantum coherent energy transfer in the Fenna-Matthews-Olson molecular aggregate under realistic physiological conditions, including vibrational fluctuations of the protein and the pigments for an experimentally determined fluctuation spectrum. We find coherence times shorter than observed experimentally. Furthermore, we determine the energy transfer current and quantify its "quantumness" as the distance of the density matrix to the classical pointer states for the energy current operator. Most importantly, we find that the energy transfer happens through a "Schrödinger-cat-like" superposition of energy current pointer states.

Quantum-Coherent Electronic Energy Transfer: Did Nature Think of It First?

Recent research suggests that electronic energy transfer in complex biological and chemical systems can involve quantum coherence, even at ambient temperature conditions. It is particularly notable that this phenomenon has been found in some photosynthetic proteins. The role of these proteins in photosynthesis is introduced. The meaning of quantum-coherent energy transfer is explained, and it is compared to Forster energy transfer. Broad, interdisciplinary questions for future work are noted. For example, how can chemists use quantum coherence in synthetic systems (perhaps in organic photovoltaics)? Why did certain photosynthetic organisms evolve to use quantum coherence in light harvesting? Are these electronic excitations entangled?

Efficiency of energy transfer in a light-harvesting system under quantum coherence

We investigate the role of quantum coherence in the efficiency of excitation transfer in a ring-hub arrangement of interacting two-level systems, mimicking a light-harvesting antenna connected to a reaction center as it is found in natural photosynthetic systems. By using a quantum jump approach, we demonstrate that in the presence of quantum coherent energy transfer and energetic disorder, the efficiency of excitation transfer from the antenna to the reaction center depends intimately on the quantum superposition properties of the initial state. In particular, we find that efficiency is sensitive to symmetric and asymmetric superposition of states in the basis of localized excitations, indicating that initial-state properties can be used as an efficiency control parameter at low temperatures.