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 a efficiency control parameter at low temperatures.

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.

We investigate multichromophoric energy transfer allowing for bath-induced fluctuations at different sites to be correlated. As a prototype system we consider a light-harvesting antenna surrounding a reaction center. We show that the interplay between quantum coherence and correlated fluctuations can generate a room temperature transfer process featuring a marked dependence on the degree of symmetry and delocalization of the initial exciton state. Our work illustrates how these quantum features could support fine tuning of energy transfer efficiencies in closely-packed natural and artificial light-harvesting complexesComment: Version published in JPC Letters. Analysis and conclusions are the same as in the original version but spectral density and reorganization energy considered correspond to more realistic values for the LH1-RC comple

Over billions of years, evolutionary pressure has facilitated the development of sophisticated and diverse light-harvesting systems in photosynthetic organisms, enabling them to adapt to a variety of habitats and light conditions. Today, driven by the need for cheap and efficient solar power, we turn to photosynthetic organisms and their light-active supramolecular assemblies for bio-inspiration. By studying natural systems, we can learn more about the basic principles behind the fine-tuned functionalities of light capture and energy transfer on the molecular level. In this review, we use ideas from evolutionary ecology and quantum mechanics to elucidate the parameters that underpin the efficient and robust light-harvesting machinery of natural light-harvesting systems. The family of antenna proteins of cryptophyte algae serves as an example to illustrate the evolutionary diversification process on a structural and consequently a photophysical level. Two-dimensional electronic spectroscopy experiments reveal the existence of coherence among vibronic levels in the initial response of light-harvesting proteins to femtosecond optical excitation. We discuss what implications quantum transport processes might have for light harvesting.

Recent evidence of electronic coherence during energy transfer in photosynthetic antenna complexes has reinvigorated the discussion of whether coherence and/or entanglement has any practical functionality for these molecular systems. Here we investigate quantitative relationships between the quantum yield of a light-harvesting complex and the distribution of entanglement among its components. Our study focusses on the entanglement yield or average entanglement surviving a time scale comparable to the average excitation trapping time. As a prototype system we consider the Fenna-Matthews-Olson (FMO) protein of green sulphur bacteria and show that there is an inverse relationship between the quantum efficiency and the average entanglement between distant donor sites. Our results suggest that longlasting electronic coherence among distant donors might help modulation of the lightharvesting function.

Recent two-dimensional electronic spectroscopy (2DES) experiments have reported evidence of coherent dynamics of electronic excitations in several light-harvesting antennae. However, 2DES uses ultrafast coherent laser pulses as an excitation source; therefore, there is a current debate on whether coherent excitation dynamics is present under natural sunlight - incoherent - illumination conditions. In this letter, we show that even if incoherent light excites an electronic state with no initial quantum superpositions among excitonic states, energy transfer can proceed quantum coherently if nonequilibrium dynamics of the phonon environment takes place. Such nonequilibrium behavior manifests itself in non-Markovian evolution of electronic excitations and is typical of many photosynthetic systems. We therefore argue that light-harvesting antennae have mechanisms that could support coherent evolution under incoherent illumination.

Strong light–matter coupling is emerging as a fascinating way to tune optical properties and modify the photophysics of molecular systems. In this work, we studied a molecular chromophore under strong coupling with the optical mode of a Fabry–Perot cavity resonant to the first electronic absorption band. Using femtosecond pump–probe spectroscopy, we investigated the transient response of the cavity-coupled molecules upon photoexcitation resonant to the upper and lower polaritons. We identified an excited state absorption from upper and lower polaritons to a state at the energy of the second cavity mode. Quantum mechanical calculations of the many-molecule energy structure of cavity polaritons suggest assignment of this state as a two-particle polaritonic state with optically allowed transitions from the upper and lower polaritons. We provide new physical insight into the role of two-particle polaritonic states in explaining transient signatures in hybrid light–matter coupling systems consistent with analogous many-body systems.

In bacterial photosynthesis light-harvesting complexes, LH2 and LH1 absorb sunlight energy and deliver it to reaction centers (RCs) with extraordinarily high efficiency. Submolecular resolution images have revealed that both the LH2:LH1 ratio, and the architecture of the photosynthetic membrane itself, adapt to light intensity. We investigate the functional implications of structural adaptations in the energy transfer performance in natural in vivo low- and high-light-adapted membrane architectures of Rhodospirillum photometricum. A model is presented to describe excitation migration across the full range of light intensities that cover states from active photosynthesis, where all RCs are available for charge separation, to saturated photosynthesis where all RCs are unavailable. Our study outlines three key findings. First, there is a critical light-energy density, below which the low-light adapted membrane is more efficient at absorbing photons and generating a charge separation at RCs, than the high-light-adapted membrane. Second, connectivity of core complexes is similar in both membranes, suggesting that, despite different growth conditions, a preferred transfer pathway is through core-core contacts. Third, there may be minimal subareas on the membrane which, containing the same LH2:LH1 ratio, behave as minimal functional units as far as excitation transfer efficiency is concerned.