Halide-metal complexes at plasmonic interfaces create new decay pathways for plasmons and excited molecules

We show that by modifying the chemical interface of silver nanoparticles (AgNPs) with halide ions, it is possible to tune the total decay rate of adsorbed excited molecules and the plasmon damping rate. Through single-molecule surface-enhanced Raman scattering and surface-enhanced fluorescence enhancement factors of crystal violet (CV) and rhodamine 6G (R6G), we show that I–-modified AgNPs (AgNPs@I) and Br–-modified AgNPs (AgNPs@Br) lead to an increase in the total decay rate of excited CV and R6G by a factor between ∼1.6–2.6, compared to Cl–-modified AgNPs (AgNPs@Cl). In addition, we found that the chemical interface damping, which characterizes the plasmon resonance decay into surface states, is stronger on AgNPs@I and AgNPs@Br when compared to AgNPs@Cl. These results point toward the formation of metal–halide surface complexes. These new interfacial states can accept electrons from both excited molecular orbitals and surface plasmon excitations, completely altering the electronic dynamics and reactivity of plasmonic interfaces

Fermi level equilibration at the metal-molecule interface in plasmonic systems

We highlight a new metal–molecule charge transfer process by tuning the Fermi energy of plasmonic silver nanoparticles (AgNPs) in situ. The strong adsorption of halide ions upshifts the Fermi level of AgNPs by up to ∼0.3 eV in the order Cl– < Br– < I–, favoring the spontaneous charge transfer to aligned molecular acceptor orbitals until charge neutrality across the interface is achieved. By carefully quantifying, experimentally and theoretically, the Fermi level upshift, we show for the first time that this effect is comparable in energy to different plasmonic effects such as the plasmoelectric effect or hot-carriers production. Moreover, by monitoring in situ the adsorption dynamic of halide ions in different AgNP–molecule systems, we show for the first time that the catalytic role of halide ions in plasmonic nanostructures depends on the surface affinity of halide ions compared to that of the target molecule

Advances in ultrafast plasmonics

In the past 20 years, we have reached a broad understanding of many light-driven phenomena in nanoscale systems. The temporal dynamics of the excited states are instead quite challenging to explore, and, at the same time, crucial to study for understanding the origin of fundamental physical and chemical processes. In this review, we examine the current state and prospects of ultrafast phenomena driven by plasmons both from a fundamental and applied point of view. This research area is referred to as ultrafast plasmonics and represents an outstanding playground to tailor and control fast optical and electronic processes at the nanoscale, such as ultrafast optical switching, single photon emission, and strong coupling interactions to tailor photochemical reactions. Here, we provide an overview of the field and describe the methodologies to monitor and control nanoscale phenomena with plasmons at ultrafast timescales in terms of both modeling and experimental characterization. Various directions are showcased, among others recent advances in ultrafast plasmon-driven chemistry and multi-functional plasmonics, in which charge, spin, and lattice degrees of freedom are exploited to provide active control of the optical and electronic properties of nanoscale materials. As the focus shifts to the development of practical devices, such as all-optical transistors, we also emphasize new materials and applications in ultrafast plasmonics and highlight recent development in the relativistic realm. The latter is a promising research field with potential applications in fusion research or particle and light sources providing properties such as attosecond duration

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