Electromagnetic field localization in nanoantennas is one of the leitmotivs that drives the development of plasmonics. The near-fields in these plasmonic nanoantennas are commonly addressed ...theoretically within classical frameworks that neglect atomic-scale features. This approach is often appropriate since the irregularities produced at the atomic scale are typically hidden in far-field optical spectroscopies. However, a variety of physical and chemical processes rely on the fine distribution of the local fields at this ultraconfined scale. We use time-dependent density functional theory and perform atomistic quantum mechanical calculations of the optical response of plasmonic nanoparticles, and their dimers, characterized by the presence of crystallographic planes, facets, vertices, and steps. Using sodium clusters as an example, we show that the atomistic details of the nanoparticles morphologies determine the presence of subnanometric near-field hot spots that are further enhanced by the action of the underlying nanometric plasmonic fields. This situation is analogue to a self-similar nanoantenna cascade effect, scaled down to atomic dimensions, and it provides new insights into the limits of field enhancement and confinement, with important implications in the optical resolution of field-enhanced spectroscopies and microscopies.
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.
A fully quantum mechanical investigation using time-dependent density functional theory reveals that the field enhancement in a coupled nanoparticle dimer can be strongly affected by nonlinear ...effects. We show that both classical as well as linear quantum mechanical descriptions of the system fail even for moderate incident light intensities. An interparticle current resulting from the strong field photoemission tends to neutralize the plasmon-induced surface charge densities on the opposite sides of the nanoparticle junction. Thus, the coupling between the two nanoparticles and the field enhancement is reduced as compared to linear theory. A substantial nonlinear effect is revealed already at incident powers of 109 W/cm2 for interparticle separation distances as large as 1 nm and down to the touching limit.
We present the optical response of two interacting metallic nanowires calculated for separation distances down to angstrom range. State-of-the-art local and nonlocal approaches are compared with full ...quantum time-dependent density functional theory calculations that give an exact account of nonlocal and tunneling effects. We find that the quantum results are equivalent to those from classical approaches when the nanoparticle separation is defined as the separation between centroids of the screening charges. This establishes a universal plasmon ruler for subnanometric distances. Such a ruler not only impacts the basis of many applications of plasmonics, but also provides a robust rule for subnanometric metrology.
Using a fully quantum mechanical approach we study the optical response of a strongly coupled metallic nanowire dimer for variable separation widths of the junction between the nanowires. The ...translational invariance of the system allows to apply the time-dependent density functional theory (TDDFT) for nanowires of diameters up to 10 nm which is the largest size considered so far in quantum modeling of plasmonic dimers. By performing a detailed analysis of the optical extinction, induced charge densities, and near fields, we reveal the major nonlocal quantum effects determining the plasmonic modes and field enhancement in the system. These effects consist mainly of electron tunneling between the nanowires at small junction widths and dynamical screening. The TDDFT results are compared with results from classical electromagnetic calculations based on the local Drude and non-local hydrodynamic descriptions of the nanowire permittivity, as well as with results from a recently developed quantum corrected model. The latter provides a way to include quantum mechanical effects such as electron tunneling in standard classical electromagnetic simulations. We show that the TDDFT results can be thus retrieved semi-quantitatively within a classical framework. We also discuss the shortcomings of classical non-local hydrodynamic approaches. Finally, the implications of the actual position of the screening charge density at the gap interfaces are discussed in connection with plasmon ruler applications at subnanometric distances.
The optical properties of a nanoparticle dimer bridged by a conductive junction depend strongly on the junction conductivity. As the conductivity increases, the bonding dimer plasmon blueshifts and ...broadens. For large conductance, a low energy charge transfer plasmon also appears in the spectra with a line width that decreases with increasing conductance. A simple physical model for the understanding of the spectral feature is presented. Our finding of a strong influence of junction conductivity on the optical spectrum suggests that plasmonic cavities might serve as probes of molecular conductance at elevated frequencies not accessible through electrical measurements.
The way conduction electrons respond to ultrafast external perturbations in low dimensional materials is at the core of the design of future devices for (opto)electronics, photodetection and ...spintronics. Highly charged ions provide a tool for probing the electronic response of solids to extremely strong electric fields localized down to nanometre-sized areas. With ion transmission times in the order of femtoseconds, we can directly probe the local electronic dynamics of an ultrathin foil on this timescale. Here we report on the ability of freestanding single layer graphene to provide tens of electrons for charge neutralization of a slow highly charged ion within a few femtoseconds. With values higher than 10
A cm
, the resulting local current density in graphene exceeds previously measured breakdown currents by three orders of magnitude. Surprisingly, the passing ion does not tear nanometre-sized holes into the single layer graphene. We use time-dependent density functional theory to gain insight into the multielectron dynamics.
Quantum effects in plasmonic systems play an important role in defining the optical response of structures with subnanometer gaps. Electron tunneling across the gaps can occur, altering both the ...far-field optical response and the near-field confinement and enhancement. In this study, we experimentally and theoretically investigate plasmon coupling in gold “nanomatryoshka” (NM) nanoparticles with different core–shell separations. Plasmon coupling effects between the core and the shell become significant when their separation decreases to 15 nm. When their separation decreases to below 1 nm, the near- and far-field properties can no longer be described by classical approaches but require the inclusion of quantum mechanical effects such as electron transport through the self-assembled monolayer of molecular junction. In addition, surface-enhanced Raman scattering measurements indicate strong electron-transport induced charge transfer across the molecular junction. Our quantum modeling provides an estimate for the AC conductances of molecules in the junction. The insights acquired from this work pave the way for the development of novel quantum plasmonic devices and substrates for surface-enhanced Raman scattering.
So far, only two interstellar objects have been observed within our Solar System. While the first one, 1I/'Oumuamua, had asteroidal characteristics, the second one, 2I/Borisov, showed clear evidence ...of cometary activity. We performed polarimetric observations of comet 2I/Borisov using the European Southern Observatory Very Large Telescope to derive the physical characteristics of its coma dust particles. Here we show that the polarization of 2I/Borisov is higher than what is typically measured for Solar System comets. This feature distinguishes 2I/Borisov from dynamically evolved objects such as Jupiter-family and all short- and long-period comets in our Solar System. The only object with similar polarimetric properties as 2I/Borisov is comet C/1995 O1 (Hale-Bopp), an object that is believed to have approached the Sun only once before its apparition in 1997. Unlike Hale-Bopp and many other comets, though, comet 2I/Borisov shows a polarimetrically homogeneous coma, suggesting that it is an even more pristine object.
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