Direct Observation of Energy Detrapping in LH1-RC Complex by Two-Dimensional Electronic Spectroscopy.

The purple bacterial core light harvesting antenna-reaction center (LH1-RC) complex is the simplest system able to achieve the entire primary function of photosynthesis. During the past decade, a variety of photosynthetic proteins were studied by a powerful technique, two-dimensional electronic spectroscopy (2DES). However, little attention has been paid to LH1-RC, although its reversible uphill energy transfer, trapping, and backward detrapping processes, represent a crucial step in the early photosynthetic reaction dynamics. Thus, in this work, we employed 2DES to study two LH1-RC complexes of Thermochromatium (Tch.) tepidum. By direct observation of detrapping, the complex reversible process was clearly identified and an overall scheme of the excitation evolution in LH1-RC was obtained.

Thickness dependent terahertz emission from cobalt thin films.

When cobalt thin films are illuminated with femtosecond laser pulses, we observe the emission of terahertz pulses. For a cobalt film thickness less than about 40 nm, the THz electric field direction rotates when the sample is rotated about the surface normal. This azimuthal angle-dependent emission is consistent with the assumption that laser-induced changes in an in-plane magnetization are responsible for the emission. For thicker layers, however, we observe the development of an azimuthal angle-independent contribution to the THz emission which we attribute to laser-induced changes in an out-of-plane magnetization component. We show that the relative contribution of this component grows when the cobalt film thickness increases. Our observations are supported by magnetic force microscopy measurements which show that for film thicknesses below 40 nm, the magnetization is predominantly in-plane whereas for thicknesses larger than 40 nm, an out-of-plane magnetization component develops.

Perturbing Open Cavities: Anomalous Resonance Frequency Shifts in a Hybrid Cavity-Nanoantenna System.

The influence of a small perturbation on a cavity mode plays an important role in fields like optical sensing, cavity quantum electrodynamics, and cavity optomechanics. Typically, the resulting cavity frequency shift directly relates to the polarizability of the perturbation. Here, we demonstrate that particles perturbing a radiating cavity can induce strong frequency shifts that are opposite to, and even exceed, the effects based on the particles' polarizability. A full electrodynamic theory reveals that these anomalous results rely on a nontrivial phase relation between cavity and nanoparticle radiation, allowing backaction via the radiation continuum. In addition, an intuitive model based on coupled mode theory is presented that relates the phenomenon to retardation. Because of the ubiquity of dissipation, we expect these findings to benefit the understanding and engineering of a wide class of systems.

Optical characterization of gold-cuprous oxide interfaces for terahertz emission applications.

We show that the interface between gold and thermally formed cuprous oxide, which emits terahertz radiation when illuminated with ultrafast femtosecond lasers, is in fact an AuCu/Cu2O interface due to the formation of the thermal diffusion alloy AuCu. The alloy enables the formation of a Schottky-barrier-like electric field near the interface which is essential to explain the THz emission from these samples. We confirm the formation of this AuCu layer by x-ray diffraction measurements, ellipsometry, and visual inspection. We determined the frequency-dependent complex refractive indices of the Cu2O and AuCu layer and verified them using reflection spectroscopy measurements. These refractive indices can be used for optimizing the thickness of Cu2O for maximum THz emission from these interfaces.

Enhanced terahertz emission by coherent optical absorption in ultrathin semiconductor films on metals.

We report on the surprisingly strong, broadband emission of coherent terahertz pulses from ultrathin layers of semiconductors such as amorphous silicon, germanium and polycrystalline cuprous oxide deposited on gold, upon illumination with femtosecond laser pulses. The strength of the emission is surprising because the materials are considered to be bad (amorphous silicon and polycrystalline cuprous oxide) or fair (amorphous germanium) terahertz emitters at best. We show that the strength of the emission is partly explained by cavity-enhanced optical absorption. This forces most of the light to be absorbed in the depletion region of the semiconductor/metal interface where terahertz generation occurs. For an excitation wavelength of 800 nm, the strongest terahertz emission is found for a 25 nm thick layer of amorphous germanium, a 40 nm thick layer of amorphous silicon and a 420 nm thick layer of cuprous oxide, all on gold. The emission from cuprous oxide is similar in strength to that obtained with optical rectification from a 300 µm thick gallium phosphide crystal. As an application of our findings we demonstrate how such thin films can be used to turn standard optical components, such as paraboloidal mirrors, into self-focusing terahertz emitters.

Revisiting the Electrochemical Nitrogen Reduction on Molybdenum and Iron Carbides: Promising Catalysts or False Positives?

The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo2C decorated carbon nanosheets, α-Mo2C nanoparticles, θ-Fe3C nanoparticles, and χ-Fe5C2 nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

Iron can be microbially extracted from Lunar and Martian regolith simulants and 3D printed into tough structural materials.

In-situ resource utilization (ISRU) is increasingly acknowledged as an essential requirement for the construction of sustainable extra-terrestrial colonies. Even with decreasing launch costs, the ultimate goal of establishing colonies must be the usage of resources found at the destination of interest. Typical approaches towards ISRU are often constrained by the mass and energy requirements of transporting processing machineries, such as rovers and massive reactors, and the vast amount of consumables needed. Application of self-reproducing bacteria for the extraction of resources is a promising approach to reduce these pitfalls. In this work, the bacterium Shewanella oneidensis was used to reduce three different types of Lunar and Martian regolith simulants, allowing for the magnetic extraction of iron-rich materials. The combination of bacterial treatment and magnetic extraction resulted in a 5.8-times higher quantity of iron and 43.6% higher iron concentration compared to solely magnetic extraction. The materials were 3D printed into cylinders and the mechanical properties were tested, resulting in a 400% improvement in compressive strength in the bacterially treated samples. This work demonstrates a proof of concept for the on-demand production of construction and replacement parts in space exploration.

The future of quantum biology.

Biological systems are dynamical, constantly exchanging energy and matter with the environment in order to maintain the non-equilibrium state synonymous with living. Developments in observational techniques have allowed us to study biological dynamics on increasingly small scales. Such studies have revealed evidence of quantum mechanical effects, which cannot be accounted for by classical physics, in a range of biological processes. Quantum biology is the study of such processes, and here we provide an outline of the current state of the field, as well as insights into future directions.

Excitonic and Vibrational Coherence in the Excitation Relaxation Process of Two LH1 Complexes as Revealed by Two-Dimensional Electronic Spectroscopy.

Ultrafast excitation relaxation within a manifold exciton state and long-lived vibrational coherence are two universal characteristics of photosynthetic antenna complexes. In this work, we studied the two-dimensional electronic spectra of two core light-harvesting (LH1) complexes of Thermochromatium (Tch.) tepidum, native Ca2+-LH1 and modified Ba2+-LH1. The role of the vibrational coherence in the exciton relaxation was revealed by comparing the two LH1 with similar structures but different electronic properties and by the evolution of the exciton and vibrational coherence as a function of temperature.

Dark States in the Light-Harvesting complex 2 Revealed by Two-dimensional Electronic Spectroscopy.

Energy transfer and trapping in the light harvesting antennae of purple photosynthetic bacteria is an ultrafast process, which occurs with a quantum efficiency close to unity. However the mechanisms behind this process have not yet been fully understood. Recently it was proposed that low-lying energy dark states, such as charge transfer states and polaron pairs, play an important role in the dynamics and directionality of energy transfer. However, it is difficult to directly detect those states because of their small transition dipole moment and overlap with the B850/B870 exciton bands. Here we present a new experimental approach, which combines the selectivity of two-dimensional electronic spectroscopy with the availability of genetically modified light harvesting complexes, to reveal the presence of those dark states in both the genetically modified and the wild-type light harvesting 2 complexes of Rhodopseudomonas palustris. We suggest that Nature has used the unavoidable charge transfer processes that occur when LH pigments are concentrated to enhance and direct the flow of energy.

Understanding the redox behaviour of PbCrO4 and its application in selective hydrogen combustion.

The performance of PbCrO(4) during reduction/oxidation cycles has been studied over the temperature range 673-873 K. During thermal treatment in an inert atmosphere, PbCrO(4) is stable up to 773 K. At higher temperatures, it decomposes rapidly and irreversibly to Pb(2)(CrO(4))O. Moreover, the redox cycling of Pb(2)(CrO(4))O is also irreversible at 873 K when the reduction semi-reaction is prolonged beyond 3 min. Taking a standard 2 min cyclic treatment, we demonstrate that the surface reduction/oxidation of Pb(2)(CrO(4))O is exothermic between 773-873 K. In contrast, the redox cycling of PbCrO(4) is endothermic at 673 K. These findings demonstrate for the first time the potential of Pb(2)(CrO(4))O as a solid oxygen reservoir for the oxidative dehydrogenation of alkanes; especially at T ≥ 773 K, where H(2) oxidation by Pb(2)(CrO(4))O is exothermic. Preliminary kinetic studies suggest that Pb(2)(CrO(4))O reduction and oxidation both proceed through a "3D diffusion of the reacting front" mechanism. Our results open up opportunities for developing energy-efficient oxidative dehydrogenation routes to commercially important olefins.