Current-controlled light scattering and asymmetric plasmon propagation in graphene

We demonstrate that plasmons in graphene can be manipulated using a DC current. A source-drain current lifts the forward/backward degeneracy of the plasmons, creating two modes with different propagation properties parallel and antiparallel to the current. We show that the propagation length of the plasmon propagating parallel to the drift current is enhanced, while the propagation length for the antiparallel plasmon is suppressed. We also investigate the scattering of light off graphene due to the plasmons in a periodic dielectric environment and we find that the plasmon resonance separates in two peaks corresponding to the forward and backward plasmon modes. The narrower linewidth of the forward propagating plasmon may be of interest for refractive index sensing and the DC current control could be used for the modulation of mid-infrared electromagnetic radiation.Comment: 5 pages, 5 figure

Optical signatures of nonlocal plasmons in graphene

We theoretically investigate under which conditions nonlocal plasmon response in monolayer graphene can be detected. To this purpose, we study optical scattering off graphene plasmon resonances coupled using a subwavelength dielectric grating. We compute the graphene conductivity using the Random Phase Approximation (RPA) obtaining a nonlocal conductivity and we calculate the optical scattering of the graphene-grating structure. We then compare this with the scattering amplitudes obtained if graphene is modeled by the local RPA conductivity commonly used in the literature. We find that the graphene plasmon wavelength calculated from the local model may deviate up to $20\%$ from the more accurate nonlocal model in the small-wavelength (large-$q$) regime. We also find substantial differences in the scattering amplitudes obtained from the two models. However, these differences in response are pronounced only for small grating periods and low temperatures compared to the Fermi temperature.Comment: Accepted for publication in Physical Review B. 15 pages, 9 figure

High-sensitivity plasmonic refractive index sensing using graphene

We theoretically demonstrate a high-sensitivity, graphene-plasmon based refractive index sensor working in the mid-infrared at room temperature. The bulk figure of merit of our sensor reaches values above $10$, but the key aspect of our proposed plasmonic sensor is its surface sensitivity which we examine in detail. We have used realistic values regarding doping level and electron relaxation time, which is the limiting factor for the sensor performance. Our results show quantitatively the high performance of graphene-plasmon based refractive index sensors working in the mid-infrared.Comment: This is an author-created, un-copyedited version of an article accepted for publication/published in 2DMaterials. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at https://doi.org/10.1088/2053-1583/aa70f

Shedding Light on the Oxidizing Properties of Spin-Flip Excited States in a CrIII Polypyridine Complex and Their Use in Photoredox Catalysis

The photoredox activity of well-known RuII complexes stems from metal-to-ligand charge transfer (MLCT) excited states, in which a ligand-based electron can initiate chemical reductions and a metal-centered hole can trigger oxidations. CrIII polypyridines show similar photoredox properties, although they have fundamentally different electronic structures. Their photoactive excited state is of spin-flip nature, differing from the electronic ground state merely by a change of one electron spin, but with otherwise identical d-orbital occupancy. We find that the driving-force dependence for photoinduced electron transfer from 10 different donors to a spin-flip excited state of a CrIII complex is very similar to that for a RuII polypyridine, and thereby validate the concept of estimating the redox potential of d3 spin-flip excited states in analogous manner as for the MLCT states of d6 compounds. Building on this insight, we use our CrIII complex for photocatalytic reactions not previously explored with this compound class, including the aerobic bromination of methoxyaryls, oxygenation of 1,1,2,2-tetraphenylethylene, aerobic hydroxylation of arylboronic acids, and the vinylation of N-phenyl pyrrolidine. This work contributes to understanding the fundamental photochemical properties of first-row transition-metal complexes in comparison to well-explored precious-metal-based photocatalysts

Developing future visions for bio-plastics substituting PET – a backcasting approach

The demand for plastics far exceeds that for any other bulk material and is expected to grow further due to global economic and population growth. Packaging is by far the largest end-user segment for plastics. Interest in bioplastics is increasing as public awareness of plastic waste accumulation in natural environ- ments increases. 2,5-Furandicarboxylic acid (FDCA) is the key monomer in the production of polyethylene 2,5-furandicarboxylate (PEF), a polymer that offers a sustainable solution to replace the commonly used polymer polyethylene terephthalate (PET). A backcasting workshop with 42 experts was held to identify current barriers and challenges that block the commercialization of FDCA-based products and to outline potential pathways toward future market diffusion. Several barriers which are strongly related to techno- logical and market-related aspects are preventing the full potential of FDCA from being unlocked. FDCA products cited in the literature are versatile and cover a wide array of niche applications. In the back- casting workshop, participants described their specific – yet highly divergent – future visions for PEF. Participants with a background in FDCA production referred mostly to developments that would need to take place in the field of FDCA applications to turn their vision into reality, while participants with a background in FDCA product development tended to refer to open issues related to FDCA synthesis. The findings of this study indicate that there is a great need for intensified cross-disciplinary communication and collaboration.publishe

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes

We present here new synthetic strategies for the isolation of a series of Ru(II) complexes with pyridyl-mesoionic carbene ligands (MIC) of the 1,2,3-triazole-5-ylidene type, in which the bpy ligands (bpy = 2,2′-bipyridine) of the archetypical [Ru(bpy)3]2+ have been successively replaced by one, two, or three pyridyl-MIC ligands. Three new complexes have been isolated and investigated via NMR spectroscopy and single-crystal X-ray diffraction analysis. The incorporation of one MIC unit shifts the potential of the metal-centered oxidation about 160 mV to more cathodic potential in cyclic voltammetry, demonstrating the extraordinary σ-donor ability of the pyridyl-MIC ligand, while the π-acceptor capacities are dominated by the bpy ligand, as indicated by electron paramagnetic resonance spectroelectrochemistry (EPR-SEC). The replacement of all bpy ligands by the pyridyl-MIC ligand results in an anoidic shift of the ligand-centered reduction by 390 mV compared to the well-established [Ru(bpy)3]2+ complex. In addition, UV/vis/NIR-SEC in combination with theoretical calculations provided detailed insights into the electronic structures of the respective redox states, taking into account the total number of pyridyl-MIC ligands incorporated in the Ru(II) complexes. The luminescence quantum yield and lifetimes were determined by time-resolved absorption and emission spectroscopy. An estimation of the excited state redox potentials conclusively showed that the pyridyl-MIC ligand can tune the photoredox activity of the isolated complexes to stronger photoreductants. These observations can provide new strategies for the design of photocatalysts and photosensitizers based on MICs

Graphene plasmons: Impurities and nonlocal effects

This work analyzes how impurities and vacancies on the surface of a graphene sample affect its optical conductivity and plasmon excitations. The disorder is analyzed in the self-consistent Green’s function formulation and nonlocal effects are fully taken into account. It is shown that impurities modify the linear spectrum and give rise to an impurity band whose position and width depend on the two parameters of our model, the density and the strength of impurities. The presence of the impurity band strongly influences the electromagnetic response and the plasmon losses. Furthermore, we discuss how the impurity-band position can be obtained experimentally from the plasmon dispersion relation and discuss this in the context of sensing

Dual Purpose Lyot Coronagraph Masks for Simultaneous High-Contrast Imaging and High-Resolution Wavefront Sensing

Directly imaging Earth-sized exoplanets with a visible-light coronagraph instrument on a space telescope will require a system that can achieve $\sim10^{-10}$ raw contrast and maintain it for the duration of observations (on the order of hours or more). We are designing, manufacturing, and testing Dual Purpose Lyot coronagraph (DPLC) masks that allow for simultaneous wavefront sensing and control using out-of-band light to maintain high contrast in the science focal plane. Our initial design uses a tiered metallic focal plane occulter to suppress starlight in the transmitted coronagraph channel and a dichroic-coated substrate to reflect out-of-band light to a wavefront sensing camera. The occulter design introduces a phase shift such that the reflected channel is a Zernike wavefront sensor. The dichroic coating allows higher-order wavefront errors to be detected which is especially critical for compensating for residual drifts from an actively-controlled segmented primary mirror. A second-generation design concept includes a metasurface to create polarization-dependent phase shifts in the reflected beam, which has several advantages including an extended dynamic range. We will present the focal plane mask designs, characterization, and initial testing at NASA's High Contrast Imaging Testbed (HCIT) facility.Comment: To appear in the Proceedings of the SPIE, Techniques and Instrumentation for Detection of Exoplanets X