Using time-dependent density functional theory, we present a fully quantum mechanical investigation of the plasmon resonances in a nanoparticle dimer as a function of interparticle separation. We ...show that for dimer separations below 1 nm quantum mechanical effects, such as electron tunneling across the dimer junction and screening, significantly modify the optical response and drastically reduce the electromagnetic field enhancements relative to classical predictions. For larger separations, the dimer plasmons are well described by classical electromagnetic theory.
Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal ...catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.
Color pixels composed of plasmonic nanostructures provide a highly promising approach for new display technologies, capable of vivid, robust coloration and incorporating the use of low-cost plasmonic ...materials, such as aluminum. Here we report a plasmonic device that can be tuned continuously across the entire visible spectrum, based on integrating a square array of aluminum nanostructures into an elastomeric substrate. By stretching the substrate in either of its two dimensions, the period and therefore the scattering color can be modified to the blue or the red of the at-rest structure, spanning the entire visible spectrum. The unique two-dimensional design of this structure enables active mechanical color tuning, under gentle elastic modulation with no more than 35% strain. We also demonstrate active image switching with this structure. This design strategy has the potential to open the door for next-generation flexible photonic devices for a wide variety of visible-light applications.
Solar illumination of broadly absorbing metal or carbon nanoparticles dispersed in a liquid produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water ...at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Sunlight-illuminated particles can also drive H2O–ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation. These phenomena can also enable important compact solar applications such as sterilization of waste and surgical instruments in resource-poor locations.
Symmetry-breaking introduced by an adjacent semi-infinite dielectric can introduce coupling and hybridization of the plasmon modes of a metallic nanostructure. This effect is particularly large for ...entities with a large contact area adjacent to the dielectric. For a nanocube, a nearby dielectric mediates an interaction between bright dipolar and dark quadrupolar modes, resulting in bonding and antibonding hybridized modes. The Fano resonance that dominates the scattering spectrum arises from the interference of these modes. This analysis provides a strategy for optimizing the sensitivity of nanostructures, whether chemically synthesized or grown by deposition methods, as high-performance localized surface plasmon resonance sensors.
Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. ...Antenna–reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna–reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO2/Pt) antenna–reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna–reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.
Aqueous solutions containing light-absorbing nanoparticles have recently been shown to produce steam at high efficiencies upon solar illumination, even when the temperature of the bulk fluid volume ...remains far below its boiling point. Here we show that this phenomenon is due to a collective effect mediated by multiple light scattering from the dispersed nanoparticles. Randomly positioned nanoparticles that both scatter and absorb light are able to concentrate light energy into mesoscale volumes near the illuminated surface of the liquid. The resulting light absorption creates intense localized heating and efficient vaporization of the surrounding liquid. Light trapping-induced localized heating provides the mechanism for low-temperature light-induced steam generation and is consistent with classical heat transfer.
Metallic structures with nanogap features have proven highly effective as building blocks for plasmonic systems, as they can provide a wide tuning range of operating frequencies and large near-field ...enhancements. Recent work has shown that quantum mechanical effects such as electron tunnelling and nonlocal screening become important as the gap distances approach the subnanometre length-scale. Such quantum effects challenge the classical picture of nanogap plasmons and have stimulated a number of theoretical and experimental studies. This review outlines the findings of many groups into quantum mechanical effects in nanogap plasmons, and discusses outstanding challenges and future directions.
The plasmon resonances in metallic nanorods are investigated using fully quantum mechanical time-dependent density functional theory. The computed optical absorption curves display well-defined ...longitudinal and transverse plasmon resonances whose energies depend on the aspect ratio of the rods, in excellent agreement with classical electromagnetic modeling. The field enhancements obtained from the quantum mechanical calculations, however, differ significantly from classical predictions for distances shorter than 0.5 nm from the nanoparticle surfaces. These deviations can be understood as arising from the nonlocal screening properties of the conduction electrons at the nanoparticle surface.
Three-dimensional chiral plasmonic nanostructures have been shown to be able to dramatically boost photon-spin selective light-matter interactions, potentially leading to novel photonics, molecular ...spectroscopy, and light-harvesting applications based on circularly polarized light. Here, we show that chiral split-ring gold nanoresonators interfaced to a wide band gap semiconductor exhibit a contrast in hot-electron transfer rate between left-handed and right-handed visible light that essentially mimics the far-field circular dichroism of the structures. We trace down the origin of this effect to the differential excitation of the thinnest part of the split-ring structures using dichroic-sensitive cathodoluminescence imaging with nanometer spatial resolution. The results highlight the intricate interplay between the near-field and far-field chiral response of a nanostructure and establishes a clear link to the emerging field of hot carrier plasmonics with numerous potential applications in photocatalysis and solar light harvesting.
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