Dynamic screening and energy loss of antiprotons colliding with excited Al clusters

We use time-dependent density functional theory to calculate the energy loss of an antiproton colliding with a small Al cluster previously excited. The velocity of the antiproton is such that non-linear effects in the electronic response of the Al cluster are relevant. We obtain that an antiproton penetrating an excited cluster transfers less energy to the cluster than an antiproton penetrating a ground state cluster. We quantify this difference and analyze it in terms of the cluster excitation spectrum.Comment: 23 pages, 4 figures, to be published in Nuclear Instruments and Methods B as a proceeding of the IISC-19 Workshop on Inelastic Ion-Surface Collision

Theoretical study of the electronic excited states in ultrathin ionic layers supported on metal surfaces: NaCl/Cu(111)

We present a theoretical study of the electronic excited states in ultrathin ionic layers supported on metal surfaces. We have studied 1, 2, 3, and 4 monolayers of NaCl on a Cu(111) surface. Energies, lifetimes, and associated wave functions of the excited states have been obtained with a joint, model potential–wave packet propagation approach. The excited state with the lowest energy has the character of an image potential state repelled from the surface by the NaCl layer. The next two states present a mixed character of image potential states and NaCl layer states corresponding to the quantization of the conduction band in the finite-size layer. We discuss the role of the layer thickness in decoupling these states from the metal surface and how it affects their lifetimeS.D.-T. gratefully acknowledges postdoctoral support from the Triangle de la Physique and the Juan de la Cierva program from the Spanish Ministerio de Ciencia e Innovación

Unveiling the anisotropic behavior of ultrafast electron transfer at the metal/organic interface

Ultrafast electron transfer between adsorbed organic molecules and metal substrates is studied. In particular, the dynamics of the active electron in the nitroethylene anion/metal-copper surface system has been followed in real time using a wave packet propagation approach, allowing a rigorous analysis of the decay of molecule-localized electronic resonances. We find that the strong coupling with the metal substrate leads to an extremely short lifetime (~1fs) of the π∗ molecular resonance. Comparison between the free-electron metal, Cu(1 0 0), and Cu(1 1 1) surfaces demonstrates that the electronic band structure of the substrate and the shape of the decaying molecular orbital lead to a highly marked anisotropy of the metal continuum states populated by resonant electron transfer from the adsorbate. This finding points at possible anisotropy effects in adsorbate–adsorbate interactions and it is of particular importance in molecular self assembly at metal surfaces, thus opening the way to a rational design of hybrid metal/organic interfaces with tailored electronic propertiesThis work was partially supported by the MICINN - Spanish Ministry of Science and Innovation - projects CTQ2016-76061-P and PID2019-110091 GB-I00, and the ‘María de Maeztu’ (CEX2018- 000805-M) Program for Centers of Excellence in R&

Ultrafast dynamics of electronic resonances in molecules adsorbed on metal surfaces: a wave packet propagation approach

We present a wave packet propagation-based method to study the electron dynamics in molecular species in the gas phase and adsorbed on metal surfaces. It is a very general method that can be employed to any system where the electron dynamics is dominated by an active electron and the coupling between the discrete and continuum electronic states is of importance. As an example, one can consider resonant molecule-surface electron transfer or molecular photoionization. Our approach is based on a computational strategy allowing incorporating ab initio inputs from quantum chemistry methods, such as density functional theory, Hartree-Fock, and coupled cluster. Thus, the electronic structure of the molecule is fully taken into account. The electron wave function is represented on a three-dimensional grid in spatial coordinates, and its temporal evolution is obtained from the solution of the time-dependent Schrödinger equation. We illustrate our method with an example of the electron dynamics of anionic states localized on organic molecules adsorbed on metal surfaces. In particular, we study resonant charge transfer from the I orbitals of three vinyl derivatives (acrylamide, acrylonitrile, and acrolein) adsorbed on a Cu(100) surface. Electron transfer between these lowest unoccupied molecular orbitals and the metal surface is extremely fast, leading to a decay of the population of the molecular anion on the femtosecond timescale. We detail how to analyze the time-dependent electronic wave function in order to obtain the relevant information on the system: The energies and lifetimes of the molecule-localized quasistationary states, their resonant wavefunctions, and the population decay channels. In particular, we demonstrate the effect of the electronic structure of the substrate on the energy and momentum distribution of the hot electrons injected into the metal by the decaying molecular resonanceThis work was partially supported by the MICINN-Spanish Ministry of Science and Innovation-projects CTQ2016-76061-P and PID2019-110091GBI00 and the “María de Maeztu” (CEX2018-000805-M) Program for Centers of Excellence in R&

Dynamic screening of a localized hole during photoemission from a metal cluster

Recent advances in attosecond spectroscopy techniques have fueled the interest in the theoretical description of electronic processes taking place in the subfemtosecond time scale. Here we study the coupled dynamic screening of a localized hole and a photoelectron emitted from a metal cluster using a semi-classical model. Electron density dynamics in the cluster is calculated with Time-Dependent Density Functional Theory and the motion of the photoemitted electron is described classically. We show that the dynamic screening of the hole by the cluster electrons affects the motion of the photoemitted electron. At the very beginning of its trajectory, the photoemitted electron interacts with the cluster electrons that pile up to screen the hole. Within our model, this gives rise to a significant reduction of the energy lost by the photoelectron. Thus, this is a velocity dependent effect that should be accounted for when calculating the average losses suffered by photoemitted electrons in metals.Comment: 15 pages, 5 figure

Active quantum plasmonics

This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license.The ability of localized surface plasmons to squeeze light and engineer nanoscale electromagnetic fields through electron-photon coupling at dimensions below the wavelength has turned plasmonics into a driving tool in a variety of technological applications, targeting novel and more efficient optoelectronic processes. In this context, the development of active control of plasmon excitations is a major fundamental and practical challenge. We propose a mechanism for fast and active control of the optical response of metallic nanostructures based on exploiting quantum effects in subnanometric plasmonic gaps. By applying an external dc bias across a narrow gap, a substantial change in the tunneling conductance across the junction can be induced at optical frequencies, which modifies the plasmonic resonances of the system in a reversible manner. We demonstrate the feasibility of the concept using time-dependent density functional theory calculations. Thus, along with two-dimensional structures, metal nanoparticle plasmonics can benefit from the reversibility, fast response time, and versatility of an active control strategy based on applied bias. The proposed electrical manipulation of light using quantum plasmonics establishes a new platform for many practical applications in optoelectronics.J.A. acknowledges support from the Spanish Ministry of Economy and Competitiveness through projects FIS2013-41184-P and 2015CD0010 of the Consejo Superior de Investigaciones Científicas scientific cooperation program for development “I-COOP LIGHT” 2015. P.N. acknowledges support from the Robert A. Welch Foundation (grant C-1222) and the Air Force Office of Science and Research (grant FA9550-15-1-0022). M.Z. acknowledges financial support from the Departamento Administrativo de Ciencia, Tecnología e Innovación–COLCIENCIAS and Facultad de Ciencias from Universidad de los Andes.Peer Reviewe

Structural phase states in nickel-titanium surface layers doped with silicon by plasma immersion ion implantation

The paper reports on a study of NiTi-based alloys used for manufacturing self-expanding intravascular stents to elucidate how the technological modes of plasma immersion ion implantation with silicon influence the chemical an