Large-scale simulations of light-matter interaction in natural photosynthetic antenna complexes containing more than one hundred thousands of chlorophyll molecules, comparable with natural size, have been performed. Photosynthetic antenna complexes present in Green sulfur bacteria and Purple bacteria have been analyzed using a radiative non-Hermitian Hamiltonian, well-known in the field of quantum optics, instead of the widely used dipole-dipole Frenkel Hamiltonian. This approach allows us to study ensembles of emitters beyond the small volume limit (system size much smaller than the absorbed wavelength), where the Frenkel Hamiltonian fails. When analyzed on a large scale, such structures display superradiant states much brighter than their single components. An analysis of the robustness to static disorder and dynamical (thermal) noise shows that exciton coherence in the whole photosynthetic complex is larger than the coherence found in its parts. This provides evidence that the photosynthetic complex as a whole plays a predominant role in sustaining coherences in the system even at room temperature. Our results allow a better understanding of natural photosynthetic antennae and could drive experiments to verify how the response to electromagnetic radiation depends on the size of the photosynthetic antenna.
Large-scale simulations of light-matter interaction in natural photosynthetic antenna complexes containing more than one hundred thousands of chlorophyll molecules, comparable with natural size, have been performed. Photosynthetic antenna complexes present in Green sulfur bacteria and Purple bacteria have been analyzed using a radiative non-Hermitian Hamiltonian, well-known in the field of quantum optics, instead of the widely used dipole-dipole Frenkel Hamiltonian. This approach allows us to study ensembles of emitters beyond the small volume limit (system size much smaller than the absorbed wavelength), where the Frenkel Hamiltonian fails. When analyzed on a large scale, such structures display superradiant states much brighter than their single components. An analysis of the robustness to static disorder and dynamical (thermal) noise shows that exciton coherence in the whole photosynthetic complex is larger than the coherence found in its parts. This provides evidence that the photosynthetic complex as a whole plays a predominant role in sustaining coherences in the system even at room temperature. Our results allow a better understanding of natural photosynthetic antennae and could drive experiments to verify how the response to electromagnetic radiation depends on the size of the photosynthetic antenna.
Recent evidence of electronic coherence during energy transfer in photosynthetic antenna complexes has reinvigorated the discussion about whether coherence and/or entanglement have 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 focuses on the entanglement yield or average entanglement surviving a time scale comparable to the average excitation trapping time. We consider the Fenna–Matthews–Olson (FMO) protein of green sulfur bacteria as a prototype system and show that there is an inverse relationship between the quantum efficiency and the average entanglement between distant donor sites. Our results suggest that long-lasting electronic coherence among distant donors might help in the modulation of the light-harvesting function.
We analyze a one-dimensional ring structure composed of many two-level systems, in the limit where only one excitation is present. The two-level systems are coupled to a common environment, where the excitation can be lost, which induces super- and subradiant behavior, an example of cooperative quantum coherent effect. We consider time-independent random fluctuations of the excitation energies. This static disorder, also called inhomogeneous broadening in literature, induces Anderson localization and is able to quench superradiance. We identify two different regimes: (i) weak opening, in which superradiance is quenched at the same critical disorder at which the states of the closed system localize; (ii) strong opening, with a critical disorder strength proportional to both the system size and the degree of opening, displaying robustness of cooperativity to disorder. Relevance to photosynthetic complexes is discussed.
Long lasting coherence in photosynthetic pigment-protein complexes has been observed even at physiological temperatures. Experiments have demonstrated quantum coherent behaviour in the long-time operation of the D-Wave quantum computer as well. Quantum coherence is the common feature between the two phenomena. An explanations for eight orders of magnitude discrepancy between the single flux qubit coherence time and the long-time quantum behaviour of an array of thousand flux qubits in the quantum computer was suggested within a theory where the flux qubits are coupled to an environment of particles called gravonons of high density of states The coherent evolution is in high dimensional spacetime and can be understood as a solution of Schroedinger's time-dependent equation. Explanations for the quantum beats observed in 2D Fourier transform electronic spectroscopy of the Fenna-Matthews-Olson (FMO) protein complex in the green sulfur bacteria are presently sought in constructing transport theories based on quantum master equations where 'good' molecular vibrations ('coloured noise') in the chlorophyll and the surrounding protein scaffold knock the exciton oscillations back into coherence. These 'good' vibrations are claimed to have developed in three billion years of natural selection. These theories, however, face the discomforting experimental observation that "attempts to scramble vibrational modes or to shift resonances with isotopic substitution miserably failed to affect the beating signals". As a possible way out of this dilemma we adopted the formalism of the quantum computation to the quantum beats in the FMO protein complex.
We explore quantum entanglement among the chlorophyll molecules in light-harvesting complex II, which is the most abundant photosynthetic antenna complex in plants containing over 50% of the world's chlorophyll molecules. Our results demonstrate that there exists robust quantum entanglement under physiological conditions for the case of a single elementary excitation. However, this nonvanishing entanglement is not unexpected because entanglement in the single-excitation manifold is conceptually the same as quantum delocalized states, which are the spectroscopically detectable energy eigenstates of the system. We discuss the impact of the surrounding environments and correlated fluctuations in electronic energies of different pigments upon quantum delocalization and quantum entanglement. It is demonstrated that investigations with tools quantifying the entanglement can provide us with more detailed information on the nature of quantum delocalization, in particular the so-called dynamic localization, which is difficult for a traditional treatment to capture.
Quantum properties like coherence and entanglement can lead to enhanced performance characteristics in a wide range of applications including quantum computation, quantum memory storage, optical sensing, and energy harvesting. Entanglement is very sensitive to static and dynamical disorder. Similarly, the generation of highly-entangled states requires strong coupling or strong driving fields. Satisfying all of these requirements is generally quite difficult. In the first part of this thesis, we present an approach to overcome these limitations through the use of exotic light-matter states in hyperbolic media which provide a new approach to control quantum correlations and interatomic interactions. We reveal a class of excited-state, long-range interactions, referred to as Super-Coulombic interactions that are singular along a material-dependent resonance angle. In practical systems, the Super-Coulombic interaction achieves dipole-dipole coupling that is orders of magnitude larger than conventional approaches, while also occurring across a large frequency bandwidth making it robust to static energy-level disorder. This unique hyperbolic response is not only naturally occurring, found in materials like h-BN, BiTe2, BiSe2, and mono-layered black phosphorus, but can also be designed with artificial nanostructured materials (metamaterials) to create the desired hyperbolic dispersion across different parts of the electromagnetic spectrum. Our theoretical prediction motivated an intense search for the effect and was confirmed by an experimental demonstration at room temperature. To obtain agreement with experimental results, we present a rigorous theoretical framework that takes into account ensemble effects, finite-sized effects, and dimensional effects that arise from confined geometries ultimately modifying the Super-Coulombic spatial scaling law. In the second part of this thesis, we solve an outstanding theoretical problem dealing with the control of resonance energy transfer in nanophotonic environments in both the incoherent and coherent coupling limits. Resonance energy transfer is a fundamental process that is the subject of intense research across all sciences. For example, in chemistry for drug delivery and chemical monitoring, in engineering for photovoltatic and up-conversion devices, and in biology for exciton transport within photosynthetic complexes. First, we consider the disordered and weak coupling limit of resonance energy transfer often encountered in chemistry. We propose new design principles for enhancing and suppressing the energy transfer rate and efficiency quantitatively captured by a simple image dipole model. Our theory explains a wide range of experimental results which have been the subject of an ongoing debate for the past 15 years. Second, we present our recent result aimed at understanding the fundamental role of entanglement and quantum coherence in resonance energy transfer. To uncover the role of these effects, we develop a unified theory of energy transfer valid from the incoherent to quantum coherent coupling regimes. Ultimately, our theory reveals a fundamental bound ηmax = γa for energy transfer efficiency arising from γd+γa the spontaneous emission rates γd and γa of the donor and acceptor. This bound provides an upper limit to the efficiency of energy transfer regardless of quantum coherence or entanglement, suggesting new design principles for achieving near-unity energy transfer efficiency in coherent systems. The result has important implications for the two-chromophore model found in photosynthetic complexes and paves the way for nanophotonic analogues of efficiency-enhancing environments mimicking biological photosynthetic systems.
This dissertation is split into two broad topics: the study of exciton transfer in a variety of organic systems, and the classical numerical simulation of quantum algorithms for chemistry. In both parts, the effects of environmental noise played an integral role. For the latter portion, a main focus was to model the implementation of a quantum algorithm on noisy quantum hardware. For the exciton studies, environmental noise was a defining characteristic of the dynamical process being studied. In both of these research areas, advanced numerical methods were often implemented for use on parallel hardware.\nThe first excitonic system we present is the chlorosome, a large photosynthetic antennae found in some species of green sulfur bacteria, containing tens of thousands of molecules. Using a method capable of simulating massive open quantum systems, we modeled the dynamics of an exciton's migration across this unusual supramolecular object. The chlorosome's unique concentric-roll structure leads to some anomalous effects with respect to initial conditions, and the study is a demonstration that these numerical methods can be directly applied to other very large excitonic simulations.\nIn a theoretical-experimental effort, our next system is a rationally designed DNA-based excitonic system. We designed a coherent "building block'' in which we demonstrated that an exciton can delocalize across multiple pseudoisocyanine molecules, which are non-covalently attached to the DNA backbone. With a combination of computational and experimental evidence, we show that these building blocks can be used to create complex DNA structures with somewhat tunable excitonic properties.\nIn the final excitonics project discussed in this dissertation, we designed a novel ``exciton gate.'' The design is similar in principle to a traditional transistor, and is the first excitonic transistor that can be activated by external light or via an auxiliary flow of excitons. This concept provides a method for a user to regulate the magnitude and direction of excitonic current in a chromophoric system. We show how to overcome the two potential challenges: short-lived second excited states and errors in the precision of orienting molecules relative to each other. Additionally, we show how a universal set of binary logic gates can be constructed, leading to universal classical computation. This new invention may lead to new developments in bioimaging, complex directed photocatalyis, phototherapeutics, and/or chemical sensing.\nIn the second portion of this dissertation, we developed two parallel software packages for the simulation of quantum algorithms. Such simulation packages are essential for the numerical study of quantum algorithms, since a viable large-scale quantum computer has not yet been built. The first package is called the Quantum High-Performance Software Testing Environment (qHiPSTER), which simulates the full Hilbert space of the quantum circuit's state. We simulated 40 qubits, which was the largest simulation of its kind at the time.\nThe second quantum computation software package, the Quantum TensOR Contraction Handler (qTorch), implements a tensor network contraction algorithm. Using the Quantum Approximate Optimization Algorithm (QAOA)/Max-Cut and the Hubbard model as test cases, we found heuristic trends that help a user determine which circuits will benefit most from a tensor network simulation approach.\nFinally, we investigated the effects of noise on chemical state preparation in quantum algorithms. Chemical state preparation is necessary for both of the main quantum algorithmic approaches to chemistry: the variational quantum eigensolver and the quantum phase estimation algorithm. Trends were elucidated with respect to mapping types (Jordan-Wigner versus Bravyi-Kitaev), noise types, and chemical properties.\nWe end with a short discussion of the future of rational excitonic design and classical simulation of quantum phenomena.