Alex W. Chin

Ultrafast long-range charge separation in organic semiconductor photovoltaic diodes.

Early Separation In photovoltaic devices, electrons excited by the absorption of light must travel across a junction, while the positively charged “holes” they leave behind effectively migrate in the opposite direction. If the electrons and holes do not separate efficiently, they can recombine and fail to produce any appreciable current. Gélinas et al. (p. 512, published online 12 December; see the Perspective by Bredas) studied this separation process by ultrafast optical absorption spectroscopy in thiophene-derived donor-fullerene acceptor systems common in organic photovoltaics and report a rate significantly faster than simple charge diffusion would suggest. The results implicate a coherent charge delocalization process, likely to involve fullerene π-electron states. Ultrafast spectroscopy shows electrons and holes separating faster than simple diffusion would imply in organic photovoltaics. [Also see Perspective by Bredas] Understanding the charge-separation mechanism in organic photovoltaic cells (OPVs) could facilitate optimization of their overall efficiency. Here we report the time dependence of the separation of photogenerated electron hole pairs across the donor-acceptor heterojunction in OPV model systems. By tracking the modulation of the optical absorption due to the electric field generated between the charges, we measure ~200 millielectron volts of electrostatic energy arising from electron-hole separation within 40 femtoseconds of excitation, corresponding to a charge separation distance of at least 4 nanometers. At this separation, the residual Coulomb attraction between charges is at or below thermal energies, so that electron and hole separate freely. This early time behavior is consistent with charge separation through access to delocalized π-electron states in ordered regions of the fullerene acceptor material.

Highly efficient energy excitation transfer in light-harvesting complexes: The fundamental role of noise-assisted transport

Excitation transfer through interacting systems plays an important role in many areas of physics, chemistry, and biology. The uncontrollable interaction of the transmission network with a noisy environment is usually assumed to deteriorate its transport capacity, especially so when the system is fundamentally quantum mechanical. Here we identify key mechanisms through which noise such as dephasing, perhaps counter intuitively, may actually aid transport through a dissipative network by opening up additional pathways for excitation transfer. We show that these are processes that lead to the inhibition of destructive interference and exploitation of line broadening effects. We illustrate how these mechanisms operate on a fully connected network by developing a powerful analytical technique that identifies the invariant (excitation trapping) subspaces of a given Hamiltonian. Finally, we show how these principles can explain the remarkable efficiency and robustness of excitation energy transfer from the light-harvesting chlorosomes to the bacterial reaction center in photosynthetic complexes and present a numerical analysis of excitation transport across the Fenna–Matthew–Olson complex together with a brief analysis of its entanglement properties. Our results show that, in general, it is the careful interplay of quantum mechanical features and the unavoidable environmental noise that will lead to an optimal system performance.

Quantum Metrology in Non-Markovian Environments

We analyze precision bounds for a local phase estimation in the presence of general, non-Markovian phase noise. We demonstrate that the metrological equivalence of product and maximally entangled states that holds under strictly Markovian dephasing fails in the non-Markovian case. Using an exactly solvable model of a physically realistic finite bandwidth dephasing environment, we demonstrate that the ensuing non-Markovian dynamics enables quantum correlated states to outperform metrological strategies based on uncorrelated states using otherwise identical resources. We show that this conclusion is a direct result of the coherent dynamics of the global state of the system and environment and therefore the obtained scaling with the number of particles, which surpasses the standard quantum limit but does not achieve Heisenberg resolution, possesses general validity that goes beyond specific models. This is in marked contrast with the situation encountered under general Markovian noise, where an arbitrarily small amount of noise is enough to restore the scaling dictated by the standard quantum limit.

Efficient Simulation of Strong System-Environment Interactions

Multicomponent quantum systems in strong interaction with their environment are receiving increasing attention due to their importance in a variety of contexts, ranging from solid state quantum information processing to the quantum dynamics of biomolecular aggregates. Unfortunately, these systems are difficult to simulate as the system-bath interactions cannot be treated perturbatively and standard approaches are invalid or inefficient. Here we combine the time-dependent density matrix renormalization group with techniques from the theory of orthogonal polynomials to provide an efficient method for simulating open quantum systems, including spin-boson models and their generalizations to multicomponent systems.

Entanglement and entangling power of the dynamics in light-harvesting complexes

Original article can be found at : http://pra.aps.org/ Copyright American Physical Society [Full text of this article is not available in the UHRA]

Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy

Singlet fission is the spin-allowed conversion of a spin-singlet exciton into a pair of spin-triplet excitons residing on neighbouring molecules. To rationalize this phenomenon, a multiexcitonic spin-zero triplet-pair state has been hypothesized as an intermediate in singlet fission. However, the nature of the intermediate states and the underlying mechanism of ultrafast fission have not been elucidated experimentally. Here, we study a series of pentacene derivatives using ultrafast two-dimensional electronic spectroscopy and unravel the origin of the states involved in fission. Our data reveal the crucial role of vibrational degrees of freedom coupled to electronic excitations that facilitate the mixing of multiexcitonic states with singlet excitons. The resulting manifold of vibronic states drives sub-100 fs fission with unity efficiency. Our results provide a framework for understanding singlet fission and show how the formation of vibronic manifolds with a high density of states facilitates fast and efficient electronic processes in molecular systems.

Exact mapping between system-reservoir quantum models and semi-infinite discrete chains using orthogonal polynomials

By using the properties of orthogonal polynomials, we present an exact unitary transformation that maps the Hamiltonian of a quantum system coupled linearly to a continuum of bosonic or fermionic modes to a Hamiltonian that describes a one-dimensional chain with only nearest-neighbor interactions. This analytical transformation predicts a simple set of relations between the parameters of the chain and the recurrence coefficients of the orthogonal polynomials used in the transformation and allows the chain parameters to be computed using numerically stable algorithms that have been developed to compute recurrence coefficients. We then prove some general properties of this chain system for a wide range of spectral functions and give examples drawn from physical systems where exact analytic expressions for the chain properties can be obtained. Crucially, the short-range interactions of the effective chain system permit these open-quantum systems to be efficiently simulated by the density matrix renormalization group methods.

Efficient biologically inspired photocell enhanced by delocalized quantum states.

Artificially implementing the biological light reactions responsible for the remarkably efficient photon-to-charge conversion in photosynthetic complexes represents a new direction for the future development of photovoltaic devices. Here, we develop such a paradigm and present a model photocell based on the nanoscale architecture and molecular elements of photosynthetic reaction centers. Quantum interference of photon absorption and emission induced by the dipole-dipole interaction between molecular excited states guarantees an enhanced light-to-current conversion and power generation for a wide range of electronic, thermal, and optical parameters for optimized dipolar geometries. This result opens a promising new route for designing artificial light-harvesting devices inspired by biological photosynthesis and quantum technologies.

Exploiting Structured Environments for Efficient Energy Transfer: The Phonon Antenna Mechanism.

A nontrivial interplay between quantum coherence and dissipative environment-driven dynamics is becoming increasingly recognized as the key for efficient energy transport in photosynthetic pigment-protein complexes, and converting these biologically inspired insights into a set of design principles that can be implemented in artificial light-harvesting systems has become an active research field. Here we identify a specific design principle, the phonon antenna, by which interpigment coherence is able to modify and optimize the way that excitations spectrally sample their local environmental fluctuations. We provide numerical simulations that suggest that the Fenna-Matthews-Olson complex of green sulfur bacteria has an excitonic structure that is close to such an optimal operating point, and place the phonon antenna concept into a broader context that leads us to conjecture that this general design principle might well be exploited in other biomolecular systems.

The nature of the low energy band of the Fenna-Matthews-Olson complex: Vibronic signatures

Based entirely upon actual experimental observations on electron-phonon coupling, we develop a theoretical framework to show that the lowest energy band of the Fenna-Matthews-Olson complex exhibits observable features due to the quantum nature of the vibrational manifolds present in its chromophores. The study of linear spectra provides us with the basis to understand the dynamical features arising from the vibronic structure in nonlinear spectra in a progressive fashion, starting from a microscopic model to finally performing an inhomogeneous average. We show that the discreteness of the vibronic structure can be witnessed by probing the diagonal peaks of the nonlinear spectra by means of a relative phase shift in the waiting time resolved signal. Moreover, we demonstrate that the photon-echo and non-rephasing paths are sensitive to different harmonics in the vibrational manifold when static disorder is taken into account. Supported by analytical and numerical calculations, we show that non-diagonal resonances in the 2D spectra in the waiting time, further capture the discreteness of vibrations through a modulation of the amplitude without any effect in the signal intrinsic frequency. This fact generates a signal that is highly sensitive to correlations in the static disorder of the excitonic energy albeit protected against dephasing due to inhomogeneities of the vibrational ensemble.