Assessing the role of interference in natural and artificial quantum dynamical processes is a crucial task in quantum information theory. To this aim, an appropriate formalism is provided by the decoherent histories framework. While this approach has been deeply explored from different theoretical perspectives, it still lacks of a comprehensive set of tools able to concisely quantify the amount of coherence developed by a given dynamics. In this paper, we introduce and test different measures of the (average) coherence present in dissipative (Markovian) quantum evolutions, at various time scales and for different levels of environmentally induced decoherence. In order to show the effectiveness of the introduced tools, we apply them to a paradigmatic quantum process where the role of coherence is being hotly debated: exciton transport in photosynthetic complexes. To spot out the essential features that may determine the performance of the transport, we focus on a relevant trimeric subunit of the Fenna-Matthews-Olson complex and we use a simplified (Haken-Strobl) model for the system-bath interaction. Our analysis illustrates how the high efficiency of environmentally assisted transport can be traced back to a quantum recoil avoiding effect on the exciton dynamics, that preserves and sustains the benefits of the initial fast quantum delocalization of the exciton over the network. Indeed, for intermediate levels of decoherence, the bath is seen to selectively kill the negative interference between different exciton pathways, while retaining the initial positive one. The concepts and tools here developed show how the decoherent histories approach can be used to quantify the relation between coherence and efficiency in quantum dynamical processes.
Assessing the role of interference in natural and artificial quantum dynamical processes is a crucial task in quantum information theory. To this aim, an appropriate formalism is provided by the decoherent histories framework. While this approach has been deeply explored from different theoretical perspectives, it still lacks of a comprehensive set of tools able to concisely quantify the amount of coherence developed by a given dynamics. In this paper, we introduce and test different measures of the (average) coherence present in dissipative (Markovian) quantum evolutions, at various time scales and for different levels of environmentally induced decoherence. In order to show the effectiveness of the introduced tools, we apply them to a paradigmatic quantum process where the role of coherence is being hotly debated: exciton transport in photosynthetic complexes. To spot out the essential features that may determine the performance of the transport, we focus on a relevant trimeric subunit of the Fenna-Matthews-Olson complex and we use a simplified (Haken-Strobl) model for the system-bath interaction. Our analysis illustrates how the high efficiency of environmentally assisted transport can be traced back to a quantum recoil avoiding effect on the exciton dynamics, that preserves and sustains the benefits of the initial fast quantum delocalization of the exciton over the network. Indeed, for intermediate levels of decoherence, the bath is seen to selectively kill the negative interference between different exciton pathways, while retaining the initial positive one. The concepts and tools here developed show how the decoherent histories approach can be used to quantify the relation between coherence and efficiency in quantum dynamical processes.
In this work, energy transfer in the photosynthetic process was studied from a quantum perspective, using the Fenna–Matthews–Olson (FMO) complex as a model. The density operator formalism and the Lindblad master equation were employed to describe the non-unitary dynamics of an open system subject to injection, extraction, and decoherence processes. A two-level system and a three-site FMO complex were analyzed, allowing the study of phenomena such as Rabi oscillations, environment-induced coherence loss, and the emergence of Environment-Assisted Quantum Transport (ENAQT). Through numerical simulations, exciton and heat currents, von Neumann entropy, global and intersite entanglement, and energy transfer efficiency were calculated. The results show that, far from being an obstacle, the interaction with the environment can enhance photosynthetic efficiency under intermediate noise regimes, thus validating the ENAQT hypothesis. This study confirms that photosynthetic systems exploit a delicate balance between coherence and decoherence to optimize energy transport.
Long-lived electronic coherences in various photosynthetic complexes at cryogenic and room temperature have generated vigorous efforts both in theory and experiment to understand their origins and explore their potential role to biological function. The ultrafast signals resulting from the experiments that show evidence for these coherences result from many contributions to the molecular polarization. Quantum process tomography (QPT) is a technique whose goal is that of obtaining the time-evolution of all the density matrix elements based on a designed set of experiments with different preparation and measurements. The QPT procedure was conceived in the context of quantum information processing to characterize and understand general quantum evolution of controllable quantum systems, for example while carrying out quantum computational tasks. We introduce our QPT method for ultrafast experiments, and as an illustrative example, apply it to a simulation of a two-chromophore subsystem of the Fenna-Matthews-Olson photosynthetic complex, which was recently shown to have long-lived quantum coherences. Our Fenna-Matthews-Olson model is constructed using an atomistic approach to extract relevant parameters for the simulation of photosynthetic complexes that consists of a quantum mechanics/molecular mechanics approach combined with molecular dynamics and the use of state-of-the-art quantum master equations. We provide a set of methods that allow for quantifying the role of quantum coherence, dephasing, relaxation and other elementary processes in energy transfer efficiency in photosynthetic complexes, based on the information obtained from the atomistic simulations, or, using QPT, directly from the experiment. The ultimate goal of the combination of this diverse set of methodologies is to provide a reliable way of quantifying the role of long-lived quantum coherences and obtain atomistic insight of their causes.
Abstract Quantum effects in photosynthetic energy transport in nature, especially for the typical Fenna-Matthews-Olson (FMO) complexes, are extensively studied in quantum biology. Such energy transport processes can be investigated as open quantum systems that blend the quantum coherence and environmental noise, and have been experimentally simulated on a few quantum devices. However, the existing experiments always lack a solid quantum simulation for the FMO energy transport due to their constraints to map a variety of issues in actual FMO complexes that have rich biological meanings. Here we successfully map the full coupling profile of the seven-site FMO structure by comprehensive characterisation and precise control of the evanescent coupling of the three-dimensional waveguide array. By applying a stochastic dynamical modulation on each waveguide, we introduce the base site energy and the dephasing term in coloured noise to faithfully simulate the power spectral density of the FMO complexes. We show our photonic model well interprets the phenomena including reorganisation energy, vibrational assistance, exciton transfer and energy localisation. We further experimentally demonstrate the existence of an optimal transport efficiency at certain dephasing strength, providing a window to closely investigate environment-assisted quantum transport.
Department ofMec hanical Engineering ,Massac husettsInstitute Tec hnolo gy 77 A venue Cambridg e MA 02139(Dated: May 18, 2008)Ener gy transfer within photosynthetic systems can display quantum effects such as delocalized exc itations.Recently , direct evidence of long-li ved coherence has been experimentally demonstrated for the dynamics ofthe Fenna-Matthe ws-Olson (FMO) protein comple x [G. S. Engel et al., Nature 446, 782 (2007)]. Ho we ver,the rele vance of quantum dynamical processes to the exciton transfer efÞcienc y is to a large extent unkno wn.Here, we de velop a general theoretical frame w ork for studying the role of quantum interference effects in ener gytransfer dynamics of molecular arrays interacting with a thermal bath. T o this end, we generalize continuous-time quantum w alks to non-unitary and temperature-dependent dynamics in Liouville space deri ved from amicroscopic Hamiltonian. Dif ferent ph ysical effects of coherence and decoherence processes are explored via auni versal measure for the ener gy transfer efÞcienc y and its susceptibility . In parti cular ,we demonstrate that forthe FMO comple x an effecti ve interplay between free Hamiltonian and thermal suctuations in the en vironmentleads to a substantial increase in ener gy transfer efÞcienc y of about 25%.
Applications of the concepts of quantum information theory are usually related to the powerful and counter-intuitive quantum mechanical effects of superposition, interference and entanglement. In this thesis, I examine the role of coherence and entanglement in complex chemical systems. The research has focused mainly on two related projects: The first project is developing a theoretical model to explain the recent ultrafast experiments on excitonic migration in photosynthetic complexes that show long-lived coherence of the order of hundreds of femtoseconds and the second project developing the Grover algorithm for global optimization of complex systems. The first part can be divided into two sections. The first section is investigating the theoretical frame about the transfer of electronic excitation energy through the Fenna-Matthews-Olson (FMO) pigment-protein complex. The new developed modified scaled hierarchical equation of motion (HEOM) approach is employed for simulating the open quantum system. The second section is investigating the evolution of entanglement in the FMO complex based on the simulation result via scaled HEOM approach. We examine the role of multipartite entanglement in the FMO complex by direct computation of the convex roof optimization for a number of different measures, including pairwise, triplet, quadruple and quintuple sites entanglement. Our results support the hypothesis that multipartite entanglement is maximum primary along the two distinct electronic energy transfer pathways. The second part of this thesis can be separated into two sections. The first section demonstrated that a modified Grover's quantum algorithm can be applied to real problems of finding a global minimum using modest numbers of quantum bits. Calculations of the global minimum of simple test functions and Lennard-Jones clusters have been carried out on a quantum computer simulator using a modified Grover's algorithm. The second section is implementing the basic quantum logical gates upon arrays of trapped ultracold polar molecules as qubits for the quantum computer. Utilized herein is the Multi-Target Optimal Control Theory (MTOCT) as a means of manipulating the initial-to-target transition probability via external laser field. The detailed calculation is applied for the SrO molecule, an ideal candidate in proposed quantum computers using arrays of trapped ultra-cold polar molecules.
It has been suggested that excitation transport in photosynthetic light-harvesting complexes features speedups analogous to those found in quantum algorithms. Here we compare the dynamics in these light-harvesting systems to the dynamics of quantum walks, in order to elucidate the limits of such quantum speedups. For the Fenna–Matthews–Olson complex of green sulfur bacteria, we show that while there is indeed speedup at short times, this is short lived (70 fs) despite longer-lived (ps) quantum coherence. Remarkably, this timescale is independent of the details of the decoherence model. More generally, we show that the distinguishing features of light-harvesting complexes not only limit the extent of quantum speedup but also reduce the rates of diffusive transport. These results suggest that quantum coherent effects in biological systems are optimized for efficiency or robustness rather than the more elusive goal of quantum speedup.