Unraveling quantum coherences mediating primary charge transfer processes in photosystem II reaction center.

Photosystem II (PSII) reaction center (RC) is a unique complex that is capable of efficiently separating electronic charges across the membrane. The primary energy- and charge-transfer (CT) processes occur on comparable ultrafast timescales, which makes it extremely challenging to understand the fundamental mechanism responsible for the near-unity quantum efficiency of the transfer. Here, we elucidate the role of quantum coherences in the ultrafast energy and CT in the PSII RC by performing two-dimensional (2D) electronic spectroscopy at the cryogenic temperature of 20 kelvin, which captures the distinct underlying quantum coherences. Specifically, we uncover the electronic and vibrational coherences along with their lifetimes during the primary ultrafast processes of energy and CT. We construct an excitonic model that provides evidence for coherent energy and CT at low temperature in the 2D electronic spectra. The principles could provide valuable guidelines for creating artificial photosystems with exploitation of system-bath coupling and control of coherences to optimize the photon conversion efficiency to specific functions.

A sensitive high repetition rate arrival time monitor for X-ray free electron lasers.

X-ray free-electron laser sources enable time-resolved X-ray studies with unmatched temporal resolution. To fully exploit ultrashort X-ray pulses, timing tools are essential. However, new high repetition rate X-ray facilities present challenges for currently used timing tool schemes. Here we address this issue by demonstrating a sensitive timing tool scheme to enhance experimental time resolution in pump-probe experiments at very high pulse repetition rates. Our method employs a self-referenced detection scheme using a time-sheared chirped optical pulse traversing an X-ray stimulated diamond plate. By formulating an effective medium theory, we confirm subtle refractive index changes, induced by sub-milli-Joule intense X-ray pulses, that are measured in our experiment. The system utilizes a Common-Path-Interferometer to detect X-ray-induced phase shifts of the optical probe pulse transmitted through the diamond sample. Owing to the thermal stability of diamond, our approach is well-suited for MHz pulse repetition rates in superconducting linear accelerator-based free-electron lasers.

Solvent Dynamics of Aqueous Halides before and after Photoionization.

Electron transfer reactions can be strongly influenced by solvent dynamics. We study the photoionization of halides in water as a model system for such reactions. There are no internal nuclear degrees of freedom in the solute, allowing the dynamics of the solvent to be uniquely identified. We simulate the equilibrium solvent dynamics for Cl-, Br-, I-, and their respective neutral atoms in water, comparing quantum mechanical/molecular mechanical (QM/MM) and classical molecular dynamics (MD) methods. On the basis of the obtained configurations, we calculate the extended X-ray absorption fine structure (EXAFS) spectra rigorously based on the MD snapshots and compare them in detail with other theoretical and experimental results available in the literature. We find our EXAFS spectra based on QM/MM MD simulations in good agreement with their experimental counterparts for the ions. Classical MD simulations for the ions lead to EXAFS spectra that agree equally well with the experiment when it comes to the oscillatory period of the signal, even though they differ from the QM/MM radial distribution functions extracted from the MD. The amplitude is, however, considerably overestimated. This suggests that to judge the reliability of theoretical simulation methods or to elucidate fine details of the atomistic dynamics of the solvent based on EXAFS spectra, the amplitude as well as the oscillatory period need to be considered. If simulations fail qualitatively, as does the classical MD for the aqueous neutral halogen atoms, the resulting EXAFS will also be strongly affected in both oscillatory period and amplitude. The good reliability of QM/MM-based EXAFS simulations, together with clear qualitative differences in the EXAFS spectra found between halides and their atomic counterparts, suggests that a combined theory and experimental EXAFS approach is suitable for elucidating the nonequilibrium solvent dynamics in the photoionization of halides and possibly also for electron transfer reactions in more complex systems.

Quantum coherent energy transport in the Fenna-Matthews-Olson complex at low temperature.

In the primary step of natural light harvesting, the solar photon energy is captured in a photoexcited electron-hole pair, or an exciton, in chlorophyll. Its conversion to chemical potential occurs in the special pair reaction center, which is reached by downhill ultrafast excited-state energy transport through a network of chromophores. Being inherently quantum, transport could in principle occur via a matter wave, with vast implications for efficiency. How long a matter wave remains coherent is determined by the intensity by which the exciton is disturbed by the noisy biological environment. The stronger this is, the stronger the electronic coupling between chromophores must be to overcome the fluctuations and phase shifts. The current consensus is that under physiological conditions, quantum coherence vanishes on the 10-fs time scale, rendering it irrelevant for the observed picosecond transfer. Yet, at low-enough temperature, quantum coherence should in principle be present. Here, we reveal the onset of longer-lived electronic coherence at extremely low temperatures of ∼20 K. Using two-dimensional electronic spectroscopy, we determine the exciton coherence times in the Fenna-Matthew-Olson complex over an extensive temperature range. At 20 K, coherence persists out to 200 fs (close to the antenna) and marginally up to 500 fs at the reaction center. It decays markedly faster with modest increases in temperature to become irrelevant above 150 K. At low temperature, the fragile electronic coherence can be separated from the robust vibrational coherence, using a rigorous theoretical analysis. We believe that by this generic principle, light harvesting becomes robust against otherwise fragile quantum effects.

Hidden Phase of the Spin-Boson Model.

A quantum two-level system immersed in a sub-Ohmic bath experiences enhanced low-frequency quantum statistical fluctuations which render the nonequilibrium quantum dynamics highly non-Markovian. Upon using the numerically exact time-evolving matrix product operator approach, we investigate the phase diagram of the polarization dynamics. In addition to the known phases of damped coherent oscillatory dynamics and overdamped decay, we identify a new third region in the phase diagram for strong coupling showing an aperiodic behavior. We determine the corresponding phase boundaries. The dynamics of the quantum two-state system herein is not coherent by itself but slaved to the oscillatory bath dynamics.

Unique Signatures of Topological Phases in Two-Dimensional THz Spectroscopy.

We develop a microscopic theory for the two-dimensional (2D) spectroscopy of one-dimensional topological superconductors. We consider a ring geometry of an archetypal topological superconductor with periodic boundary conditions, bypassing energy-specific differences caused by topologically protected or trivial boundary modes that are hard to distinguish. We show numerically and analytically that the cross-peak structure of the 2D spectra carries unique signatures of the topological phases of the chain. Our work reveals how 2D spectroscopy can identify topological phases in bulk properties.

Ultrafast Charge Transfer and Relaxation at a Donor-Acceptor Interface.

The efficiency of charge separation in organic photovoltaic materials is crucially determined by the underlying dynamics of the charge transfer (CT) excitons and their dissociation into free electrons and holes. To unravel the main principles of the underlying mechanism on a molecular level, we construct a toy model of electronically coupled donors interacting with a manifold of CT exciton states. In particular, we set up a ladder of CT site energies to model the exciton dissociation. To mimic the complexity of the exciton dynamics at the donor-acceptor interface, the electronic CT manifold is designed to include two vibrational modes that are vibronically coupled to the excitons. We examine the impact of the electronic and vibrational coherences and the structure of the vibronic manifold on the transfer efficiency and charge recombination. Optimal configurations of the vibronic CT manifold are revealed. In particular, the rate of charge recombination can be minimized when the transient dynamics are carefully explored. Such a toy model can be used as a guide for the design of organic materials for efficient photovoltaic devices.

Bosonic Continuum Theory of One-Dimensional Lattice Anyons.

Anyons with arbitrary exchange phases exist on 1D lattices in ultracold gases. Yet, known continuum theories in 1D do not match. We derive the continuum limit of 1D lattice anyons via interacting bosons. The theory maintains the exchange phase periodicity fully analogous to 2D anyons. This provides a mapping between experiments, lattice anyons, and continuum theories, including Kundu anyons with a natural regularization as a special case. We numerically estimate the Luttinger parameter as a function of the exchange angle to characterize long-range signatures of the theory and predict different velocities for left- and right-moving collective excitations.

Rotating edge-field driven processing of chiral spin textures in racetrack devices.

Topologically distinct magnetic structures like skyrmions, domain walls, and the uniformly magnetized state have multiple applications in logic devices, sensors, and as bits of information. One of the most promising concepts for applying these bits is the racetrack architecture controlled by electric currents or magnetic driving fields. In state-of-the-art racetracks, these fields or currents are applied to the whole circuit. Here, we employ micromagnetic and atomistic simulations to establish a concept for racetrack memories free of global driving forces. Surprisingly, we realize that mixed sequences of topologically distinct objects can be created and propagated over far distances exclusively by local rotation of magnetization at the sample boundaries. We reveal the dependence between chirality of the rotation and the direction of propagation and define the phase space where the proposed procedure can be realized. The advantages of this approach are the exclusion of high current and field densities as well as its compatibility with an energy-efficient three-dimensional design.

Photoinduced Vibrations Drive Ultrafast Structural Distortion in Lead Halide Perovskite.

The success of organic-inorganic perovskites in optoelectronics is dictated by the complex interplay between various underlying microscopic phenomena. The structural dynamics of organic cations and the inorganic sublattice after photoexcitation are hypothesized to have a direct effect on the material properties, thereby affecting the overall device performance. Here, we use ultrafast heterodyne-detected two-dimensional (2D) electronic spectroscopy to reveal impulsively excited vibrational modes of methylammonium (MA) lead iodide perovskite, which drive the structural distortion after photoexcitation. Vibrational analysis of the measured data allows us to monitor the time-evolved librational motion of the MA cation along with the vibrational coherences of the inorganic sublattice. Wavelet analysis of the observed vibrational coherences reveals the coherent generation of the librational motion of the MA cation within ∼300 fs complemented with the coherent evolution of the inorganic skeletal motion. To rationalize this observation, we employed the configuration interaction singles (CIS), which support our experimental observations of the coherent generation of librational motions in the MA cation and highlight the importance of the anharmonic interaction between the MA cation and the inorganic sublattice. Moreover, our advanced theoretical calculations predict the transfer of the photoinduced vibrational coherence from the MA cation to the inorganic sublattice, leading to reorganization of the lattice to form a polaronic state with a long lifetime. Our study uncovers the interplay of the organic cation and inorganic sublattice during formation of the polaron, which may lead to novel design principles for the next generation of perovskite solar cell materials.

Intermolecular vibrations mediate ultrafast singlet fission.

Singlet fission is a spin-allowed exciton multiplication process in organic semiconductors that converts one spin-singlet exciton to two triplet excitons. It offers the potential to enhance solar energy conversion by circumventing the Shockley-Queisser limit on efficiency. We study the primary steps of singlet fission in a pentacene film by using a combination of TG and 2D electronic spectroscopy complemented by quantum chemical and nonadiabatic dynamics calculations. We show that the coherent vibrational dynamics induces the ultrafast transition from the singlet excited electronic state to the triplet-pair state via a degeneracy of potential energy surfaces, i.e., a multidimensional conical intersection. Significant vibronic coupling of the electronic wave packet to a few key intermolecular rocking modes in the low-frequency region connect the excited singlet and triplet-pair states. Along with high-frequency local vibrations acting as tuning modes, they open a new channel for the ultrafast exciton transfer through the resulting conical intersection.

Time-Resolved Probing of the Nonequilibrium Structural Solvation Dynamics by the Time-Dependent Stokes Shift.

The time-dependent fluorescence Stokes shift monitors the relaxation of the polarization of a polar solvent in the surroundings of a photoexcited solute molecule but also the structural variation of the solute following photoexcitation and the subsequent molecular charge redistribution. Here, we formulate a simple nonequilibrium quantum theory of solvation for an explicitly time-dependent continuous solvent. The time-dependent solvent induces nonequilibrium fluctuations on the solvent dynamics which are directly reflected in different time components in the time-dependent Stokes shift. We illustrate the structural dynamics in the presence of an explicitly time-dependent solvent by the example of a dynamically shrinking solute which leads to a bimodal Stokes shift. Interestingly, both contributions are mutually coupled. Furthermore, we can explain a prominent long-tail decay of the Stokes shift associated with slow structural dynamical variations.

Quantum biology revisited.

Photosynthesis is a highly optimized process from which valuable lessons can be learned about the operating principles in nature. Its primary steps involve energy transport operating near theoretical quantum limits in efficiency. Recently, extensive research was motivated by the hypothesis that nature used quantum coherences to direct energy transfer. This body of work, a cornerstone for the field of quantum biology, rests on the interpretation of small-amplitude oscillations in two-dimensional electronic spectra of photosynthetic complexes. This Review discusses recent work reexamining these claims and demonstrates that interexciton coherences are too short lived to have any functional significance in photosynthetic energy transfer. Instead, the observed long-lived coherences originate from impulsively excited vibrations, generally observed in femtosecond spectroscopy. These efforts, collectively, lead to a more detailed understanding of the quantum aspects of dissipation. Nature, rather than trying to avoid dissipation, exploits it via engineering of exciton-bath interaction to create efficient energy flow.

Intramolecular vibrations enhance the quantum efficiency of excitonic energy transfer.

We study the impact of underdamped intramolecular vibrational modes on the efficiency of the excitation energy transfer in a dimer in which each state is coupled to its own underdamped vibrational mode and, in addition, to a continuous background of environmental modes. For this, we use the numerically exact hierarchy equation of motion approach. We determine the quantum yield and the transfer time in dependence of the vibronic coupling strength, and in dependence of the damping of the incoherent background. Moreover, we tune the vibrational frequencies out of resonance with the excitonic energy gap. We show that the quantum yield is enhanced by up to 10% when the vibrational frequency of the donor is larger than at the acceptor. The vibronic energy eigenstates of the acceptor acquire then an increased density of states, which leads to a higher occupation probability of the acceptor in thermal equilibrium. We can conclude that an underdamped vibrational mode which is weakly coupled to the dimer fuels a faster transfer of excitation energy, illustrating that long-lived vibrations can, in principle, enhance energy transfer, without involving long-lived electronic coherence.

Charge Transfer through Redox Molecular Junctions in Nonequilibrated Solvents.

Molecular conduction operating in dielectric solvent environments is often described using kinetic rates based on the Marcus theory of electron transfer at a molecule-metal electrode interface. However, the successive nature of charge transfer in such a system implies that the solvent does not necessarily reach equilibrium in such processes. Here we generalize the theory to account for solvent nonequilibrium and consider a molecular junction consisting of an electronic donor-acceptor system coupled to two metallic electrodes and placed in a polarizable solvent. We determine the nonequilbrium distribution of the solvent by solving diffusion equations in the strong- and weak-friction limits and calculate the charge current and its fluctuating behavior. In extreme limits, the absence of the solvent or fast solvent relaxation, the charge-transfer statistics is Poissonian, while it becomes correlated by the dynamic solvent between these limits. A Kramers-like turnover of the nonequilibrium current as a function of the solvent damping is found. Finally, we propose a way to tune the solvent-induced damping using geometrical control of the solvent dielectric response in nanostructured solvent channels.

Does electronic coherence enhance anticorrelated pigment vibrations under realistic conditions?

The light-harvesting efficiency of a photoactive molecular complex is largely determined by the properties of its electronic quantum states. Those, in turn, are influenced by molecular vibrational states of the nuclear degrees of freedom. Here, we reexamine two recently formulated concepts that a coherent vibronic coupling between molecular states would either extend the electronic coherence lifetime or enhance the amplitude of the anticorrelated vibrational mode at longer times. For this, we study a vibronically coupled dimer and calculate the nonlinear two-dimensional (2D) electronic spectra that directly reveal electronic coherence. The time scale of electronic coherence is initially extracted by measuring the antidiagonal bandwidth of the central peak in the 2D spectrum at zero waiting time. Based on the residual analysis, we identify small-amplitude long-lived oscillations in the cross-peaks, which, however, are solely due to groundstate vibrational coherence, regardless of having resonant or off-resonant conditions. Our studies neither show an enhancement of the electronic quantum coherence nor an enhancement of the anticorrelated vibrational mode by the vibronic coupling under ambient conditions.

Winding Up Quantum Spin Helices: How Avoided Level Crossings Exile Classical Topological Protection.

A magnetic helix can be wound into a classical Heisenberg chain by fixing one end while rotating the other one. We show that in quantum Heisenberg chains of finite length, the magnetization slips back to the trivial state beyond a finite turning angle. Avoided level crossings thus undermine classical topological protection. Yet, for special values of the axial Heisenberg anisotropy, stable spin helices form again, which are nonlocally entangled. Away from these sweet spots, spin helices can be stabilized dynamically or by dissipation. For half-integer spin chains of odd length, a spin slippage state and its Kramers partner define a qubit with a nontrivial Berry connection.

Ultrafast Energy Transfer in Excitonically Coupled Molecules Induced by a Nonlocal Peierls Phonon.

Molecular vibration can influence exciton transfer via either a local (intramolecular) Holstein or a nonlocal (intermolecular) Peierls mode. We show that a strong vibronic coupling to a nonlocal mode dramatically speeds up the transfer by opening an additional transfer channel. This Peierls channel is rooted in the formation of a conical intersection of the excitonic potential energy surfaces. For increasing Peierls coupling, the electronically coherent transfer for weak coupling turns into an incoherent transfer of a localized exciton through the intersection for strong coupling. The interpretation in terms of a conical intersection intuitively explains recent experiments of ultrafast energy transfer in photosynthetic and photovoltaic molecular systems.

Spectroscopic Signatures of the Dynamical Hydrophobic Solvation Shell Formation.

When a hydrophilic solute in water is suddenly turned into a hydrophobic species, for instance, by photoionization, a layer of hydrated water molecules forms around the solute on a time scale of a few picoseconds. We study the dynamic buildup of the hydration shell around a hydrophobic solute on the basis of a time-dependent dielectric continuum model. Information about the solvent is spectroscopically extracted from the relaxation dynamics of a test dipole inside a static Onsager sphere in the nonequilibrium solvent. The growth process is described phenomenologically within two approaches. First, we consider a time-dependent thickness of the hydration layer that grows from zero to a finite value over a finite time. Second, we assume a time-dependent complex permittivity within a finite layer region around the Onsager sphere. The layer is modeled as a continuous dielectric with a much slower fluctuation dynamics. We find a time-dependent frequency shift down to the blue of the resonant absorption of the dipole, together with a dynamically decreasing line width, as compared to bulk water. The blue shift reflects the work performed against the hydrogen-bonded network of the bulk solvent and is a directly measurable quantity. Our results are in agreement with an experiment on the hydrophobic solvation of iodine in water.

Quantum mechanical response to a driven Caldeira-Leggett bath.

We determine the frequency-dependent response characteristics of a quantum system to a driven Caldeira-Leggett bath. The bath degrees of freedom are explicitly driven by an external time-dependent force, in addition to the direct time-dependent forcing of the system itself. After general considerations of driven Caldeira-Leggett baths, we consider the Rubin model of a chain of quantum particles coupled by linear springs as an important model of a quantum dissipative system. We show that in the presence of time-dependent driving of the chain, this model can be mapped to a quantum system which couples to a driven Caldeira-Leggett bath. The effect of the bath driving is captured by a time-dependent force on the central system, which is, in principle, non-Markovian in nature. We study two specific examples, the exactly solvable case of a harmonic potential and a quantum two-state system for which we assume a weak system-bath coupling. We evaluate the dynamical response to a periodic driving of the system and the bath. The dynamic susceptibility is shown to be altered qualitatively by the bath drive: The dispersive part is enhanced at low frequencies and acquires a maximum at zero frequency. The absorptive part develops a shoulder-like behavior in this frequency regime. These features seem to be generic for quantum systems in a driven Caldeira-Leggett bath.