Localized surface plasmon resonances (LSPRs) have recently been identified in extremely diluted electron systems obtained by doping semiconductor quantum dots. Here we investigate the role that different surface effects, namely electronic spill-out a
nd diffuse surface scattering, play in the optical properties of these ultra-low electron density nanosystems. Diffuse scattering originates from imperfections or roughness at a microscopic scale on the surface. Using an electromagnetic theory that describes this mechanism in conjunction with a dielectric function including the quantum size effect, we find that the LSPRs show an oscillatory behavior both in position and width for large particles and a strong blueshift in energy and an increased width for smaller radii, consistent with recent experimental results for photodoped ZnO nanocrystals. We thus show that the commonly ignored process of diffuse surface scattering is a more important mechanism affecting the plasmonic properties of ultra-low electron density nanoparticles than the spill-out effect.
Nanometer-sized metal particles exhibit broadening of the localized surface plasmon resonance (LSPR) in comparison to its value predicted by the classical Mie theory. Using our model for the LSPR dependence on non-local surface screening and size qua
ntization, we quantitatively relate the observed plasmon width to the nanoparticle radius $R$ and the permittivity of the surrounding medium $epsilon_m$. For Ag nanospheres larger than 8 nm only the non-local dynamical effects occurring at the surface are important and, up to a diameter of 25 nm, dominate over the bulk scattering mechanism. Qualitatively, the LSPR width is inversely proportional to the particle size and has a nonmonotonic dependence on the permittivity of the host medium, exhibiting for Ag a maximum at $epsilon_mapprox2.5$. Our calculated LSPR width is compared with recent experimental data.
Electron and energy transfer processes between an atom or molecule and a surface are extremely important for many applications in physics and chemistry. Therefore a profound understanding of these processes is essential in order to analyze a large va
riety of physical systems. The microscopic description of the two-electron Auger processes, leading to neutralization/ionization of an ion/neutral atom in front of a solid surface, has been a long-standing problem. It can be dated back to the 1950s when H. D. Hagstrum proposed to use the information contained in the spectrum of the electrons emitted during the neutralization of slow noble gas ions as a surface analytical tool complementing photoelectron spectroscopy. However, only recently a comprehensive description of the Auger neutralization mechanism has been achieved by the combined efforts of theoretical and experimental methods. In this article we review the theoretical models for this problem, stressing how their outcome compare with experimental results. We also analyze the inverse problem of Auger ionization. We emphasize the understanding of the key quantities governing the processes and outline the challenges remaining. This opens new perspectives for future developments of theoretical and experimental work in this field.
We present a combined theoretical approach to study the nonequilibrium transport properties of nanoscale systems coupled to metallic electrodes and exhibiting strong electron-phonon interactions. We use the Keldysh Green function formalism to general
ize beyond linear theory in the applied voltage an equation of motion method and an interpolative self-energy approximation previously developed in equilibrium. We analyze the specific characteristics of inelastic transport appearing in the intensity versus voltage curves and in the conductance, providing qualitative criteria for the sign of the step-like features in the conductance. Excellent overall agreement between both approaches is found for a wide range of parameters.
