Signature of Quantum Coherence in the Exciton Energy Pathways of the LH2 Photosynthetic Complex.

Unraveling the energy transfer pathways in photosynthetic complexes is an important step toward understanding their structure-function interplay. Here, we use an open quantum systems approach to investigate energy transfer within the LH2 photosynthetic apparatus and its dependence on environmental conditions. We find that energy transfer pathways strongly depend on the environment-induced dephasing time. A comparison between the computational results and experiments performed on similar systems demonstrates that quantum coherences are present in these systems under physiological conditions and have an important role in shaping the energy transfer pathways. Moreover, our calculations indicate that relatively simple spectroscopy experiments can be used to detect traces of quantum coherence. Finally, our results suggest that quantum coherence may play a role in photosynthesis, but not in enhancing the efficiency as was previously suggested.

Temperature-dependence of the chirality-induced spin selectivity effect-Experiments and theory.

The temperature-dependence of the chirality-induced spin selectivity (CISS) effect can be used to discriminate between different theoretical proposals for the mechanism of the CISS effect. Here, we briefly review key experimental results and discuss the effect of temperature in different models for the CISS effect. We then focus on the recently suggested spinterface mechanism and describe the different possible effects temperature can have within this model. Finally, we analyze in detail recent experimental results presented in the work of Qian et al. [Nature 606, 902-908 (2022)] and demonstrate that, contrary to the original interpretation by the authors, these data actually indicate that the CISS effect increases with decreasing temperature. Finally, we show how the spinterface model can accurately reproduce these experimental results.

Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity.

Stereochemistry has an essential role in organic synthesis, biological catalysis and physical processes. In situ chirality identification and asymmetric synthesis are non-trivial tasks, especially for single-molecule systems. However, going beyond the chiral characterization of a large number of molecules (which inevitably leads to ensemble averaging) is crucial for elucidating the different properties induced by the chiral nature of the molecules. Here we report direct monitoring of chirality variations during a Michael addition followed by proton transfer and keto-enol tautomerism in a single molecule. Taking advantage of the chirality-induced spin selectivity effect, continuous current measurements through a single-molecule junction revealed in situ chirality variations during the reaction. Chirality identification at a high sensitivity level provides a promising tool for the study of symmetry-breaking reactions and sheds light on the origin of the chirality-induced spin selectivity effect itself.

Spinterface chirality-induced spin selectivity effect in bio-molecules.

The chirality-induced spin selectivity (CISS) effect, namely the dependence of current through a chiral molecule on spin of the electron, was discovered over two decades ago, and has been suggested for various spin- and chirality-related applications. Yet, quite surprisingly, its physical origin remains elusive, and no theoretical description can quantitatively describe it. Here, we propose a theory for the CISS effect in bio-molecular junctions, based on the interplay between spin-orbit coupling in the electrodes, molecular chirality and spin-transfer torque across the electrode-molecule interface. This theory leads to the first ever quantitative analysis of experimental data, and provides insights into the origin of the CISS effect. The theory presented here can be used to analyze past experiments and to design new experiments, which may lead to deeper understanding of what is considered one of the outstanding problems in molecular electronics and nano-scale transport.

Emergence and Dynamical Stability of a Charge Time-Crystal in a Current-Carrying Quantum Dot Simulator.

Periodically driven open quantum systems that never thermalize exhibit a discrete time-crystal behavior, a nonequilibrium quantum phenomenon that has shown promise in quantum information processing applications. Measurements of time-crystallinity are currently limited to (magneto-) optical experiments in atom-cavity systems and spin-systems making it an indirect measurement. We theoretically show that time-crystallinity can be measured directly in the charge-current from a spin-less Hubbard ladder, which can be simulated on a quantum-dot array. We demonstrate that one can dynamically tune the system out and then back on a time-crystal phase, proving its robustness against external forcings. These findings motivate further theoretical and experimental efforts to simulate the time-crystal phenomena in current-carrying nanoscale systems.

Photothermal nonlinearity in plasmon-assisted photocatalysis.

Understanding the intricate relationship between illumination and temperature in metallic nano-particles is crucial for elucidating the role of illumination in various physical processes which rely on plasmonic enhancement but are also sensitive to temperature. Recent studies have shown that the temperature rise in optically thick ensembles of metal nanoparticles under intense illumination is dominated by the thermal conductivity of the host, rather than by the optical properties of the metal or the host. Here, we show that the temperature dependence of the thermal conductivity of the host dominates the nonlinear photothermal response of these systems. In particular, this dependence typically causes the temperature rise to become strongly sublinear, reaching even several tens of percent. We then show that this effect can explain experimental observations in several recent plasmon-assisted photocatalysis experiments. Under certain conditions, we show that thermal emission may also contribute to photothermal nonlinearity. This shows that any claim for the dominance of non-thermal electrons in plasmon-assisted photocatalysis must account first for this photothermal nonlinear mechanism.

Distinguishing Thermal from Nonthermal ("Hot") Carriers in Illuminated Molecular Junctions.

The search for the signature of nonthermal (so-called "hot") electrons in illuminated plasmonic nanostructures requires detailed understanding of the nonequilibrium electron distribution under illumination, as well as a careful design of the experimental system employed to distinguish nonthermal electrons from thermal ones. Here, we provide a theory for using plasmonic molecular junctions to achieve this goal. We show how nonthermal electrons can be measured directly and separately from the unavoidable thermal response and discuss the relevance of our theory to recent experiments.

Spinterface Origin for the Chirality-Induced Spin-Selectivity Effect.

When electrons are injected through a chiral molecule, the resulting current may become spin polarized. This effect, known as the chirality-induced spin-selectivity (CISS) effect, has been suggested to emerge due to the interplay between spin-orbit interactions and the chirality within the molecule. However, such explanations require unrealistically large values for the molecular spin-orbit interaction. Here, we present a theory for the CISS effect based on the interplay between spin-orbit interactions in the electrode, the chirality of the molecule (which induces a solenoid field), and spin-transfer torque at the molecule-electrode interface. Using a mean-field calculation with simple models for the molecular junction, we show that our phenomenological theory can qualitatively account for all key experimental observations, most importantly the magnitude of the CISS with realistic parameters. We also provide a set of predictions which can be readily tested experimentally.

Theory of "Hot" Photoluminescence from Drude Metals.

We provide a complete quantitative theory for light emission from Drude metals under continuous wave illumination, based on our recently derived steady-state nonequilibrium electron distribution. We show that the electronic contribution to the emission exhibits a dependence on the emission frequency which is very similar to the energy dependence of the nonequilibrium distribution, and characterize different scenarios determining the measurable emission line shape. This enables the identification of experimentally relevant situations, where the emission lineshapes deviate significantly from predictions based on the standard theory (namely, on the photonic density of states), and enables the differentiation between cases where the emission scales with the metal object surface or with its volume. We also provide an analytic description (which is absent from the literature) of the (polynomial) dependence of the metal emission on the electric field, its dependence on the pump laser frequency, and its nontrivial exponential dependence on the electron temperature, both for the Stokes and anti-Stokes regimes. Our results imply that the emission does not originate from either Fermion statistics (due to e-e interactions), and even though one could have expected the emission to follow boson statistics due to involvement of photons (as in Planck's Black Body emission), it turns out that it deviates from that form as well. Finally, we resolve the arguments associated with the effects of electron and lattice temperatures on the emission, and which of them can be extracted from the anti-Stokes emission.

Do photosynthetic complexes use quantum coherence to increase their efficiency? Probably not.

Answering the titular question has become a central motivation in the field of quantum biology, ever since the idea was raised following a series of experiments demonstrating wave-like behavior in photosynthetic complexes. Here, we report a direct evaluation of the effect of quantum coherence on the efficiency of three natural complexes. An open quantum systems approach allows us to simultaneously identify their level of "quantumness" and efficiency, under natural physiological conditions. We show that these systems reside in a mixed quantum-classical regime, characterized by dephasing-assisted transport. Yet, we find that the change in efficiency at this regime is minute at best, implying that the presence of quantum coherence does not play a substantial role in enhancing efficiency. However, in this regime, efficiency is independent of any structural parameters, suggesting that evolution may have driven natural complexes to their parameter regime to "design" their structure for other uses.

Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis.

Recent experiments claimed that the catalysis of reaction rates in numerous bond-dissociation reactions occurs via the decrease of activation barriers driven by non-equilibrium ("hot") electrons in illuminated plasmonic metal nanoparticles. Thus, these experiments identify plasmon-assisted photocatalysis as a promising path for enhancing the efficiency of various chemical reactions. Here, we argue that what appears to be photocatalysis is much more likely thermo-catalysis, driven by the well-known plasmon-enhanced ability of illuminated metallic nanoparticles to serve as heat sources. Specifically, we point to some of the most important papers in the field, and show that a simple theory of illumination-induced heating can explain the extracted experimental data to remarkable agreement, with minimal to no fit parameters. We further show that any small temperature difference between the photocatalysis experiment and a control experiment performed under external heating is effectively amplified by the exponential sensitivity of the reaction, and is very likely to be interpreted incorrectly as "hot" electron effects.

Reply to the 'Comment on "Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis"' by P. Jain, Chem. Sci., 2020, 11, DOI: 10.1039/D0SC02914A.

In his Comment to our paper "Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis", Jain correctly points out that using an Arrhenius fit to the reaction rate is not enough to distinguish thermal from non-thermal effects.

"Hot" electrons in metallic nanostructures-non-thermal carriers or heating?

Understanding the interplay between illumination and the electron distribution in metallic nanostructures is a crucial step towards developing applications such as plasmonic photocatalysis for green fuels, nanoscale photodetection and more. Elucidating this interplay is challenging, as it requires taking into account all channels of energy flow in the electronic system. Here, we develop such a theory, which is based on a coupled Boltzmann-heat equations and requires only energy conservation and basic thermodynamics, where the electron distribution, and the electron and phonon (lattice) temperatures are determined uniquely. Applying this theory to realistic illuminated nanoparticle systems, we find that the electron and phonon temperatures are similar, thus justifying the (classical) single-temperature models. We show that while the fraction of high-energy "hot" carriers compared to thermalized carriers grows substantially with illumination intensity, it remains extremely small (on the order of 10-8). Importantly, most of the absorbed illumination power goes into heating rather than generating hot carriers, thus rendering plasmonic hot carrier generation extremely inefficient. Our formulation allows for the first time a unique quantitative comparison of theory and measurements of steady-state electron distributions in metallic nanostructures.

Comment on "Quantifying hot carrier and thermal contributions in plasmonic photocatalysis".

Zhou et al (Reports, 5 October 2018, p. 69) claim to have proven dominance of "hot" electrons over thermal effects in plasmonic photocatalysis. We identify experimental flaws that caused overestimation of the hot carrier contribution. As an alternative interpretation, we fully reproduce their data using a purely thermal Arrhenius law with a fixed activation energy and intensity-dependent heating.

Assistance of metal nanoparticles in photocatalysis - nothing more than a classical heat source.

In a recent paper, we derived a self-consistent theory of the steady-state electron distribution of a metal under continuous wave illumination which treats thermal and non-thermal effects on the same footing. Here, we re-derive the main analytical results of that study from very simple arguments, and draw a series of conclusions which contradict claims made in previous studies of the steady-state distribution. In particular, we show that the faster chemical reactions reported in many previous papers are extremely unlikely to originate from high energy non-thermal electrons. Instead, the faster reactions very likely originate from a purely thermal effect.

Vibration-Assisted and Vibration-Hampered Excitonic Quantum Transport.

The interplay between excitons and vibrations is considered to be a key factor in determining the exciton-transfer properties in light-harvesting complexes. Here we study this interplay theoretically in a model for exciton transport, composed of two chromophores coupled to an exciton source and sink in the presence of vibrations. We consider two cases that show qualitatively distinct transport features. In the first, the vibrations are global and affect the two chromophores simultaneously. In the second case, the vibrations are localized on each chromophore. For global vibrations, the current exhibits antiresonances as a function of the chromophore energy difference, which are due to exciton-polaron interference. For local vibrations, on the contrary, the currents show tunneling resonances at multiples of the vibration energy. Counterintuitively, both effects increase with increasing temperature. Our results demonstrate that an environment can either assist or hamper exciton transport and is in accord with the current understanding of energy transfer in natural exciton-transfer complexes.

Universal Origin for Environment-Assisted Quantum Transport in Exciton Transfer Networks.

Environment-assisted quantum transport (ENAQT) is the possibility of an external environment to enhance transport efficiency of quantum particles. This idea has generated much excitement over recent years, especially due to the experimentally motivated possibility of ENAQT in photosynthetic exciton transfer complexes. Many theoretical calculations have shown ENAQT, but the explanations for its origin differ, and a universal explanation has been elusive. Here we demonstrate a universal origin for ENAQT in quantum networks with a dephasing environment, based on a relation between exciton current and occupation within a Markovian open quantum system approach. We show that ENAQT appears due to two competing processes, namely, the tendency of dephasing to make the exciton population uniform, and the formation of an exciton density gradient, defined by the source and the sink. Furthermore, we find a geometric condition on the network for the appearance of ENAQT, relevant to natural and artificial systems.

Topological quantization of energy transport in micro- and nano-mechanical lattices.

Topological effects typically discussed in the context of quantum physics are emerging as one of the central paradigms of physics. Here, we demonstrate the role of topology in energy transport through dimerized micro- and nano-mechanical lattices in the classical regime, i.e., essentially "masses and springs". We show that the thermal conductance factorizes into topological and nontopological components. The former takes on three discrete values and arises due to the appearance of edge modes that prevent good contact between the heat reservoirs and the bulk, giving a length-independent reduction of the conductance. In essence, energy input at the boundary mostly stays there, an effect robust against disorder and nonlinearity. These results bridge two seemingly disconnected disciplines of physics, namely topology and thermal transport, and suggest ways to engineer thermal contacts, opening a direction to explore the ramifications of topological properties on nanoscale technology.

Photoconductance from Exciton Binding in Molecular Junctions.

We report on a theoretical analysis and experimental verification of a mechanism for photoconductance, the change in conductance upon illumination, in symmetric single-molecule junctions. We demonstrate that photoconductance at resonant illumination arises due to the Coulomb interaction between the electrons and holes in the molecular bridge, so-called exciton-binding. Using a scanning tunneling microscopy break junction technique, we measure the conductance histograms of perylene tetracarboxylic diimide (PTCDI) molecules attached to Au-electrodes, in the dark and under illumination, and show a significant and reversible change in conductance, as expected from the theory. Finally, we show how our description of the photoconductance leads to a simple design principle for enhancing the performance of molecular switches.