Using coherence to enhance function in chemical and biophysical systems.

Coherence phenomena arise from interference, or the addition, of wave-like amplitudes with fixed phase differences. Although coherence has been shown to yield transformative ways for improving function, advances have been confined to pristine matter and coherence was considered fragile. However, recent evidence of coherence in chemical and biological systems suggests that the phenomena are robust and can survive in the face of disorder and noise. Here we survey the state of recent discoveries, present viewpoints that suggest that coherence can be used in complex chemical systems, and discuss the role of coherence as a design element in realizing function.

Strong Quantum Darwinism and Strong Independence are Equivalent to Spectrum Broadcast Structure.

How the objective everyday world emerges from the underlying quantum behavior of its microscopic constituents is an open question at the heart of the foundations of quantum mechanics. Quantum Darwinism and spectrum broadcast structure are two different frameworks providing key insight into this question. Recent works, however, indicate these two frameworks can lead to conflicting predictions on the objectivity of the state of a system interacting with an environment. Here, we provide a resolution to this issue by defining strong quantum Darwinism and proving that it is equivalent to spectrum broadcast structure when combined with strong independence of the subenvironments. We further show that strong quantum Darwinism is sufficient and necessary to signal state objectivity without the requirement of strong independence. Our Letter unveils the deep connection between strong quantum Darwinism and spectrum broadcast structure, thereby making fundamental progress toward understanding and solving the emergence of classicality from the quantum world. Together they provide us a sharper understanding of the transition in terms of state structure, geometry, and quantum and classical information.

Transient synchronisation and quantum coherence in a bio-inspired vibronic dimer.

Synchronisation is a collective phenomenon widely investigated in classical oscillators and, more recently, in quantum systems. However it remains unclear what features distinguish synchronous behaviour in these two scenarios. Recent works have shown that investigating synchronisation dynamics in open quantum systems can give insight into this issue. Here we study transient synchronisation in a bio-inspired vibronic dimer, where electronic excitation dynamics is mediated by coherent interactions with intramolecular vibrational modes. We show that the synchronisation dynamics of local mode displacements exhibit a rich behaviour which arises directly from the distinct time-evolutions of different vibronic quantum coherences. Furthermore, our study shows that coherent energy transport in this bio-inspired system is concomitant with the emergence of positive synchronisation between mode displacements. Our work provides further understanding of the relations between quantum coherence and synchronisation in open quantum systems and suggests an interesting role for coherence in biomolecules, that of promoting synchronisation of vibrational motions driven out of thermal equilibrium.

Isolating the chiral contribution in optical two-dimensional chiral spectroscopy using linearly polarized light.

The full development of mono- or multi-dimensional time-resolved spectroscopy techniques incorporating optical activity signals has been strongly hampered by the challenge of identifying the small chiral signals over the large achiral background. Here we propose a new methodology to isolate chiral signals removing the achiral background from two commonly used configurations for performing two-dimensional optical spectroscopy, known as BOXCARS and gradient assisted photon echo spectroscopy (GRAPES). It is found that in both cases an achiral signal from an isotropic system can be completely eliminated by small manipulations of the relative angles between the linear polarizations of the four input laser pulses. Starting from the formulation of a perturbative expansion of the signal in the angle between the beams and the propagation axis, we derive analytic expressions that can be used to estimate how to change the polarization angles of the four pulses to minimize achiral contributions in the studied configurations. The generalization to any other possible experimental configurations has also been discussed.

Coherence specific signal detection via chiral pump-probe spectroscopy.

We examine transient circular dichroism (TRCD) spectroscopy as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system.

Molecular basis of the exciton-phonon interactions in the PE545 light-harvesting complex.

Long-lived quantum coherences observed in several photosynthetic pigment-protein complexes at low and at room temperatures have generated a heated debate over the impact that the coupling of electronic excitations to molecular vibrations of the relevant actors (pigments, proteins and solvents) has on the excitation energy transfer process. In this work, we use a combined MD and QM/MMPol strategy to investigate the exciton-phonon interactions in the PE545 light-harvesting complex by computing the spectral densities for each pigment and analyzing their consequences in the exciton dynamics. Insights into the origin of relevant peaks, as well as their differences among individual pigments, are provided by correlating them with normal modes obtained from a quasi-harmonic analysis of the motions sampled by the pigments in the complex. Our results indicate that both the protein and the solvent significantly modulate the intramolecular vibrations of the pigments thus playing an important role in promoting or suppressing certain exciton-phonon interactions. We also find that these low-frequency features are largely smoothed out when the spectral density is averaged over the complex, something difficult to avoid in experiments that underscores the need to combine theory and experiment to understand the origin of quantum coherence in photosynthetic light-harvesting.

Comment on "Excitons in molecular aggregates with Lévy-type disorder: anomalous localization and exchange broadening of optical spectra".

A Comment on the Letter by A. Eisfeld et al. Phys. Rev. Lett. 105, 137402 (2010). The authors of the Letter offer a Reply.

Phonon-mediated path-interference in electronic energy transfer.

We present a formalism to quantify the contribution of path-interference in phonon-mediated electronic energy transfer. The transfer rate between two molecules is computed by considering the quantum mechanical amplitudes associated with pathways connecting the initial and final sites. This includes contributions from classical pathways, but also terms arising from interference of different pathways. We treat the vibrational modes coupled to the molecules as a non-Markovian harmonic oscillator bath, and investigate the correction to transfer rates due to the lowest-order interference contribution. We show that depending on the structure of the harmonic bath, the correction due to path-interference may have a dominant vibrational or electronic character, and can make a notable contribution to the transfer rate in the steady state.

The fundamental role of quantized vibrations in coherent light harvesting by cryptophyte algae.

The influence of fast vibrations on energy transfer and conversion in natural molecular aggregates is an issue of central interest. This article shows the important role of high-energy quantized vibrations and their non-equilibrium dynamics for energy transfer in photosynthetic systems with highly localized excitonic states. We consider the cryptophyte antennae protein phycoerythrin 545 and show that coupling to quantized vibrations, which are quasi-resonant with excitonic transitions is fundamental for biological function as it generates non-cascaded transport with rapid and wider spatial distribution of excitation energy. Our work also indicates that the non-equilibrium dynamics of such vibrations can manifest itself in ultrafast beating of both excitonic populations and coherences at room temperature, with time scales in agreement with those reported in experiments. Moreover, we show that mechanisms supporting coherent excitonic dynamics assist coupling to selected modes that channel energy to preferential sites in the complex. We therefore argue that, in the presence of strong coupling between electronic excitations and quantized vibrations, a concrete and important advantage of quantum coherent dynamics is precisely to tune resonances that promote fast and effective energy distribution.

Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation.

We derive a many-site version of the non-Markovian time-convolutionless polaron master equation [Jang et al., J. Chem Phys. 129, 101104 (2008)] to describe electronic excitation dynamics in multichromophoric systems. By treating electronic and vibrational degrees of freedom in a combined frame (polaron frame), this theory is capable of interpolating between weak and strong exciton-phonon coupling and is able to account for initial non-equilibrium bath states and spatially correlated environments. Besides outlining a general expression for the expected value of any electronic system observable in the original frame, we also discuss implications of the Markovian and Secular approximations highlighting that they need not hold in the untransformed frame despite being strictly satisfied in the polaron frame. The key features of the theory are illustrated using as an example a four-site subsystem of the Fenna-Mathews-Olson light-harvesting complex. For a spectral density including a localised mode, we show that oscillations of site populations may only be observed when non-equilibrium bath effects are taken into account. Furthermore, we illustrate how this formalism allows us to identify the electronic and vibrational components of the oscillatory dynamics.

Energy transfer in light-adapted photosynthetic membranes: from active to saturated photosynthesis.

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.

On the performance of a photosystem II reaction centre-based photocell.

The photosystem II reaction centre is the photosynthetic complex responsible for oxygen production on Earth. Its water splitting function is particularly favoured by the formation of a stable charge separated state via a pathway that starts at an accessory chlorophyll. Here we envision a photovoltaic device that places one of these complexes between electrodes and investigate how the mean current and its fluctuations depend on the microscopic interactions underlying charge separation in the pathway considered. Our results indicate that coupling to well resolved vibrational modes does not necessarily offer an advantage in terms of power output but can lead to photo-currents with suppressed noise levels characterizing a multi-step ordered transport process. Besides giving insight into the suitability of these complexes for molecular-scale photovoltaics, our work suggests a new possible biological function for the vibrational environment of photosynthetic reaction centres, namely, to reduce the intrinsic current noise for regulatory processes.

Non-classicality of the molecular vibrations assisting exciton energy transfer at room temperature.

Advancing the debate on quantum effects in light-initiated reactions in biology requires clear identification of non-classical features that these processes can exhibit and utilize. Here we show that in prototype dimers present in a variety of photosynthetic antennae, efficient vibration-assisted energy transfer in the sub-picosecond timescale and at room temperature can manifest and benefit from non-classical fluctuations of collective pigment motions. Non-classicality of initially thermalized vibrations is induced via coherent exciton-vibration interactions and is unambiguously indicated by negativities in the phase-space quasi-probability distribution of the effective collective mode coupled to the electronic dynamics. These quantum effects can be prompted upon incoherent input of excitation. Our results therefore suggest that investigation of the non-classical properties of vibrational motions assisting excitation and charge transport, photoreception and chemical sensing processes could be a touchstone for revealing a role for non-trivial quantum phenomena in biology.

Coherent Energy Transfer under Incoherent Light Conditions.

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.

Lessons from nature about solar light harvesting.

Solar fuel production often starts with the energy from light being absorbed by an assembly of molecules; this electronic excitation is subsequently transferred to a suitable acceptor. For example, in photosynthesis, antenna complexes capture sunlight and direct the energy to reaction centres that then carry out the associated chemistry. In this Review, we describe the principles learned from studies of various natural antenna complexes and suggest how to elucidate strategies for designing light-harvesting systems. We envisage that such systems will be used for solar fuel production, to direct and regulate excitation energy flow using molecular organizations that facilitate feedback and control, or to transfer excitons over long distances. Also described are the notable properties of light-harvesting chromophores, spatial-energetic landscapes, the roles of excitonic states and quantum coherence, as well as how antennas are regulated and photoprotected.

Robust one-step catalytic machine for high fidelity anticloning and W-state generation in a multiqubit system.

We propose a physically realizable machine which can either generate multiparticle W-like states, or implement high-fidelity 1-->M (M=1,2,...infinity) anticloning of an arbitrary qubit state, in a single step. This universal machine acts as a catalyst in that it is unchanged after either procedure, effectively resetting itself for its next operation. It possesses an inherent immunity to decoherence. Most importantly in terms of practical multiparty quantum communication, the machine's robustness in the presence of decoherence actually increases as the number of qubits M increases.