RESUMEN
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 π* 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 resonance.
RESUMEN
The dynamics of ultrafast electron currents triggered by femtosecond laser pulse irradiation of narrow gaps in a plasmonic dimer is studied using quantum mechanical Time-Dependent Density Functional Theory (TDDFT). The electrons are injected into the gap due to the optical field emission from the surfaces of the metal nanoparticles across the junction. Further evolution of the electron currents in the gap is governed by the locally enhanced electric fields. The combination of TDDFT and classical modelling of the electron trajectories allows us to study the quiver motion of the electrons in the gap region as a function of the Carrier Envelope Phase (CEP) of the incident pulse. In particular, we demonstrate the role of the quiver motion in establishing the CEP-sensitive net electric transport between nanoparticles.
RESUMEN
: 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.
RESUMEN
The high stability of a low temperature (9 K) scanning tunneling microscope junction is used to precisely adjust the enhancement of an external pulsed vacuum ultraviolet (VUV) laser. The ensuing VUV optical-field strength is mapped on an hydrogenated Si(100) surface by imprinting locally one-photon atomic scale hydrogen desorption. Subsequent to irradiation, topography of the Si(100):H surface at the reacted area revealed a desorption spot with unprecedented atomic precision. Our results show that the shapes, positions, and sizes of the desorption spots are correlated to the calculated optical-field structure, offering real control of the optical-field distribution at molecular scale.
RESUMEN
The present theoretical study shows that a double chain of Cu metal atoms adsorbed on a Cu(111) metal surface can guide an excited electron for distances exceeding 10 nm. The nanostructure appears to be quasi-decoupled from the substrate and thus to act as a nanowire. The origin of the above phenomenon is the interference between the decay of the quasistationary 1D sp-band states localized on each chain. This allows to approach the situation of the formation of bound states in the continuum first discussed in quantum systems by von Neumann and Wigner.
RESUMEN
We present a joint experimental-theoretical study of the one-dimensional band of excited electronic states with sp character localized on Cu nanowires supported on a Cu(111) surface. Energy dispersion and lifetime of these states have been obtained, allowing the determination of the mean distance traveled by an excited electron along the nanowire before it escapes into the substrate. We show that a Cu nanowire supported on a Cu(111) surface can guide a one-dimensional electron flux over a short distance and thus can be considered as a possible component for nanoelectronics devices.
