Atomistic Study of Energy Funneling in the Light-Harvesting Complex of Green Sulfur Bacteria

Phototrophic organisms such as plants, photosynthetic bacteria, and algae use microscopic complexes of pigment molecules to absorb sunlight. Within the light-harvesting complexes, which frequently have several functional and structural subunits, the energy is transferred in the form of molecular excitations with very high efficiency. Green sulfur bacteria are considered to be among the most efficient light-harvesting organisms. Despite multiple experimental and theoretical studies of these bacteria, the physical origin of the efficient and robust energy transfer in their light-harvesting complexes is not well understood. To study excitation dynamics at the systems level, we introduce an atomistic model that mimics a complete light-harvesting apparatus of green sulfur bacteria. The model contains approximately 4000 pigment molecules and comprises a double wall roll for the chlorosome, a baseplate, and six Fenna-Matthews-Olson trimer complexes. We show that the fast relaxation within functional subunits combined with the transfer between collective excited states of pigments can result in robust energy funneling to the initial excitation conditions and temperature changes. Moreover, the same mechanism describes the coexistence of multiple time scales of excitation dynamics frequently observed in ultrafast optical experiments. While our findings support the hypothesis of supertransfer, the model reveals energy transport through multiple channels on different length scales.Chemistry and Chemical BiologyPhysic

Probing ultrafast energy transfer between excitons and plasmons in the ultrastrong coupling regime

Cataloged from PDF version of article.We investigate ultrafast energy transfer between excitons and plasmons in ensembles of core-shell type nanoparticles consisting of metal core covered with a concentric thin J-aggregate (JA) shell. The high electric field localization by the Ag nanoprisms and the high oscillator strength of the JAs allow us to probe this interaction in the ultrastrong plasmon-exciton coupling regime. Linear and nonlinear optical properties of the coupled system have been measured using transient absorption spectroscopy revealing that the hybrid system shows half-plasmonic and half-excitonic properties. The tunability of the nanoprism plasmon resonance provides a flexible platform to study the dynamics of the hybrid state in a broad range of wavelengths. (C) 2014 AIP Publishing LLC

Organic-Inorganic Composites of Semiconductor Nanocrystals for Efficient Excitons

Cataloged from PDF version of article.Nanocomposites of colloidal semiconductor nanocrystals integrated into conjugated polymers are the key to soft-material hybrid optoelectronics, combining advantages of both plastics and particles. Synergic combination of the favorable properties in the hybrids of colloidal nanocrystals and conjugated polymers offers enhanced performance and new functionalities in light-generation and light-harvesting applications, where controlling and mastering the excitonic interactions at the nanoscale are essential. In this Perspective, we highlight and critically consider the excitonic interactions in the organic inorganic nanocomposites to achieve highly efficient exciton transfer through rational design of the nanocomposites. The use of strong excitonic interactions in optoelectronic devices can trigger efficiency breakthroughs in hybrid optoelectronics

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales [Formula: see text]100 fs. Today's understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes

Quantum Simulator of an Open Quantum System Using Superconducting Qubits: Exciton Transport in Photosynthetic Complexes

Open quantum system approaches are widely used in the description of physical, chemical and biological systems. A famous example is electronic excitation transfer in the initial stage of photosynthesis, where harvested energy is transferred with remarkably high efficiency to a reaction center. This transport is affected by the motion of a structured vibrational environment, which makes simulations on a classical computer very demanding. Here we propose an analog quantum simulator of complex open system dynamics with a precisely engineered quantum environment. Our setup is based on superconducting circuits, a well established technology. As an example, we demonstrate that it is feasible to simulate exciton transport in the Fenna–Matthews–Olson photosynthetic complex. Our approach allows for a controllable single-molecule simulation and the investigation of energy transfer pathways as well as non-Markovian noise-correlation effects.Chemistry and Chemical Biolog

Coherent manipulation of non-thermal spin order in optical nuclear polarization experiments

Time resolved measurements of Optical Nuclear Polarization (ONP) have been performed on hyperpolarized triplet states in molecular crystals created by light excitation. Transfer of the initial electron polarization to nuclear spins has been studied in the presence of radiofrequency excitation; the experiments have been performed with different pulse sequences using different doped molecular systems. The experimental results clearly demonstrate the dominant role of coherent mechanisms of spin order transfer, which manifest themselves in well pronounced oscillations. These oscillations are of two types, precessions and nutations, having characteristic frequencies, which are the same for the different molecular systems and the pulse sequences applied. Hence, precessions and nutations constitute a general feature of polarization transfer in ONP experiments. In general, coherent manipulation of spin order transfer creates a powerful resource for improving the performance of the ONP method, which paves the way to strong signal enhancement in nuclear magnetic resonance

FOB-SH: Fragment orbital-based surface hopping for charge carrier transport in organic and biological molecules and materials

We introduce a fragment orbital-based fewest switches surface hopping method, FOB-SH, designed to efficiently simulate charge carrier transport in strongly fluctuating condensed phase systems such as organic semiconductors and biomolecules. The charge carrier wavefunction is expanded and the electronic Hamiltonian constructed in a set of singly occupied molecular orbitals of the molecular sites that mediate the charge transfer. Diagonal elements of the electronic Hamiltonian (site energies) are obtained from a force field, whereas the off-diagonal or electronic coupling matrix elements are obtained using our recently developed analytic overlap method. We derive a general expression for the exact forces on the adiabatic ground and excited electronic state surfaces from the nuclear gradients of the charge localized electronic states. Applications to electron hole transfer in a model ethylene dimer and through a chain of ten model ethylenes validate our implementation and demonstrate its computational efficiency. On the larger system, we calculate the qualitative behaviour of charge mobility with change in temperature T for different regimes of the intermolecular electronic coupling. For small couplings, FOB-SH predicts a crossover from a thermally activated regime at low temperatures to a band-like transport regime at higher temperatures. For higher electronic couplings, the thermally activated regime disappears and the mobility decreases according to a power law. This is interpreted by a gradual loss in probability for resonance between the sites as the temperature increases. The polaron hopping model solved for the same system gives a qualitatively different result and underestimates the mobility decay at higher temperatures. Taken together, the FOB-SH methodology introduced here shows promise for a realistic investigation of charge carrier transport in complex organic, aqueous, and biological systems

Generalized Theory of Forster-Type Nonradiative Energy Transfer in Nanostructures with Mixed Dimensionality

Cataloged from PDF version of article.Forster-type nonradiative energy transfer (NRET) is widely used, especially utilizing nanostructures in different combinations and configurations. However, the existing well-accepted Forster theory is only for the case of a single particle serving as a donor together with another particle serving as an acceptor. There are also other special cases previously studied; however, there is no complete picture and unified understanding. Therefore, there is a strong need for a complete theory that models Forster-type NRET for the cases of mixed dimensionality including all combinations and configurations. We report a generalized theory for the Forster-type, NRET, which includes the derivation of the effective dielectric function due to the donor in different confinement geometries and the derivation of transfer rates distance dependencies due to the acceptor in different confinement geometries, resulting in a complete picture and understanding of the mixed dimensionality

Ultrafast Hyperspectral Transient Absorption Spectroscopy: Application to Single Layer Graphene

We describe the basic principles and the experimental implementation of the hyperspectral transient absorption technique, based on femtosecond laser sources. In this technique the samples were optically “pumped” using the femtosecond tunable pulse delivered by an Optical Parametric Amplifier, and “probed” for changes in transmission in a broad spectral range with a “white light” laser-generated supercontinuum. The spectra were collected by a pair of multichannel detectors which allowed retrieval of the absorbance change in a wide spectral range in one time. The use of the supercontinuum probe introduced artifacts in the measured 2D data set which could be corrected with a proper calibration of the chirp. The configuration with crossed polarization for pump and probe pulse extended the spectral measured range above and below the pump energy within the same experiment. We showed the versatility of the technique by applying it to the investigation of the charge carrier dynamics in two-dimensional single layer graphene

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.Engineering and Physical Sciences Research Council, Winton Programme for the Physics of Sustainability, University of Cambridge, China Scholarship Council, SoltechThis is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b0513